Metal-siloxane-silanol(ate) compound as gel catalyst

ABSTRACT

The invention relates to the use of at least one metal-siloxane-silanol(ate) compound for selective catalysis of the gel reaction in a system for the production of polyurethanes, preferably of unfoamed polyurethanes, flexible foams or rigid foams and/or in the two-component (2K) system according to the invention, and to processes for producing foamed or unfoamed polyurethanes, especially flexible foams or rigid foams, and to use in the CASE sector (coatings, adhesives, sealants and elastomers), furniture, mattresses, car seats, seal materials or acoustic materials, for insulation of district heating pipes, tanks and pipelines, and for production of all kinds of refrigeration units. In a further aspect, the invention relates to unfoamed polyurethanes, flexible foams and/or rigid foams each produced through the inventive use of at least one metal-siloxane-silanol(ate) compound for selective catalysis of the gel reaction.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a National Stage of International Application No.PCT/EP2020/057877 filed on Mar. 20, 2020, claiming priority based onEuropean Patent Application No. 19165363.3 filed on Mar. 26, 2019 andEuropean Patent Application No. 19206679.3 filed on Oct. 31, 2019.

The present invention relates to the field of production ofpolyurethanes, especially by means of two-component (2K) systems,preferably to the production of unfoamed polyurethanes and/or of rigidfoams and flexible foams (PU foams), and to the use thereof in CASEsectors (coatings, adhesives, sealants and elastomers). The inventionespecially relates to the use of a gel catalyst in the production ofpolyurethanes, and also to the composition thereof and to processes forproducing polyurethanes.

One of the most important chemical reactions of relevance in theproduction of polyurethanes, especially of rigid and flexible foams,coatings, adhesives, sealant materials and elastomers (CASE), is thereaction of an isocyanate-containing component with a compoundcontaining an active hydrogen, as is the case, for example, in polyolsand/or water. According to the progression of the reaction and choice ofcatalyst, it is possible to catalyse what is called the gel reaction(1). The urethane linkage through reaction of an isocyanate-containingcomponent with an isocyanate-reactive component (e.g.hydroxy-functionalized polymer or polyol) permits the formation ofpolyurethanes

R—NCO+HO—R′→R—NH—CO—OR′(gel reaction)  (1)

The reaction of an isocyanate-containing component with water, bycontrast, leads to formation of an unstable carbamic acid that breaksdown to give a primary amine and CO₂ (2).

R—NCO+H—OH→[R—NH—CO—OH]→R—NH2+CO₂↑(blow reaction)  (2)

R′—NH2+R—NCO→R′—NH—CO—NH—R  (3)

The primary amine formed reacts with an isocyanate-containing componentto give symmetric urea derivatives.

This reaction (2) is referred to as blow reaction. The CO₂ that formsassumes the function here of a blowing gas, for example in theproduction of polyurethane foams.

In the case of production of unfoamed polyurethanes, this reaction isundesirable. It is generally desirable for the person skilled in the artto be able to control reactions and the progression thereof. This isfundamentally also the case in the production of rigid and flexiblefoams. In that case too, it may be advantageous to control the blowreaction, such that, for example, no foaming or no excessive orundesirable foaming of the material takes place.

The person skilled in the art is aware, in particular, of organic tincomplexes, especially dibutyltin dilaurate (DBTL) and tertiary amines,especially triethylenediamine (DABCO (=TEDA)) catalysts in polyurethaneproduction.

Unwanted blow reactions can also set in on account of residual moisturein the reactants (for example in polyols, fillers, solvents, auxiliariesetc.) or on account of ambient humidity in the production and curingprocess. It is known that this can be countered by the use of waterscavengers or desiccants. The use of additional raw materials—that areusually hazardous to health—such as water scavengers, for examplevinyltrimethoxysilane (VTMO or Dynasilan®) leads to a further increasein production costs.

It is accordingly an object of the invention to provide an improvedprocess for producing polyurethanes.

This object is achieved according to claim 1. Advantageous developmentsare the subject of the dependent claims or of the further independentclaims.

The core of the invention is to use the new and surprising finding thatmetal-siloxane-silanol(ate) compounds selectively catalyse the gelreaction for the production of polyurethanes, especially of unfoamedpolyurethanes, flexible foams or rigid foams. One aspect of theinvention is thus the use of metal-siloxane-silanol(ate) compounds asgel catalyst.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts the foaming characteristics of the elastomer products EP1(reference) and EP4-EP6 (water content 0.1%).

FIG. 2 depicts the foaming characteristics of the elastomer products EP1(reference) and EP7-EP9 (water content 0.2%).

FIG. 3 depicts the foaming characteristics of the elastomer products EP1(reference) and EP10-EP12 (water content 0.4%).

FIG. 4 depicts the foaming characteristics of the elastomer products EP1(reference) and EP13-EP15 (water content 0.6%).

FIG. 5 depicts the foaming characteristics of the elastomer products EP1(reference) and EP16-EP18 (water content 0.8%).

In the context of the present invention, the term “gel catalyst” (or“gelation catalyst”) is understood to mean a catalyst thatpreferentially catalyses the gel reaction (1) compared to the blowreaction, i.e. urethane linkage by reaction of an isocyanate-containingcomponent with an isocyanate-reactive component (hydroxy-functionalizedpolymer or polyol). The formation of the urethane bond (R—NH—CO—OR′), inthe presence of at least one metal-siloxane-silanol(ate) compound, isaccordingly preferred over the formation of the urea bond(R′—NH—CO—NH—R).

The term “selectivity” (or “gel/blow reaction selectivity”), in thecontext of the present invention, thus describes the property of acatalyst of the degree to which it preferentially catalyses the gelreaction over the blow reaction. If neither of the reactions ispreferred, the selectivity is 1, i.e. the ratio of gel reaction to blowreaction is 1:1. The greater the value, the more the catalyst catalysesthe gel reaction compared to the blow reaction.

In a preferred embodiment of the invention, themetal-siloxane-silanol(ate) compound has a selectivity of >1,preferably >5, more preferably >10, further preferably >30, mostpreferably >40. Preferred metal-siloxane-silanol(ate) compounds arespecified below. Particular preference is given to themetal-siloxane-silanol(ate) compounds according to claim 17, especiallycompounds according to claim 18. In claim 18, particular preference isgiven to the compounds TiPOSS and SnPOSS.

The selectivity of the metal-siloxane-silanol(ate) compounds becameapparent to the inventors for the first time through comparison with thepreviously known catalysts DBTL and DABCO. In comparative experiments(Example I below), test compositions (EP1-EP18) for unfoamedpolyurethanes that differ in their water content and the respectivecatalyst were used. The inventors found here that, in the presence ofTiPOSS, the blow reaction only set in at a higher amount of watercompared to the customary catalysts. The onset of the blow reaction wasidentified by the foaming (by the gaseous CO2↑ formed) of the material.This means that, when TiPOSS is used in the production of polyurethanes,the Shore hardness and density of the material remain essentiallyunchanged in the presence of water within particular limits.

The selectivity of catalysts for the gel reaction with respect to theblow reaction in the production of polyurethanes can be verified by anessay according to Example I below.

In addition, the person skilled in the art is aware of methods ofdetermining the selectivity of catalysts in the production ofpolyurethanes, for example the titration method according to Farkasdescribed below in Example III (A. Farkas and K. G. Flynn, J. Am. Chem.Soc., 82, 642, 1960) or the method according to R. van Maris et al. (J.Cel. Plastics, 41, 305-322, 2005). The titration method compares therespective reaction during a standardized conversion of an isocyanatecomponent with a diol component (including alcohol) in the presence ofdifferent catalysts.

It is fundamentally the case that the properties of the resultingpolyurethanes can be more accurately adjusted with more specificsteering and control of the gel reaction and/or blow reaction. Thus, theinventive use of metal-siloxane-silanol(ate) compounds enables, forexample, more constant densities in unfoamed polyurethanes, or elevatedtensile strengths in foamed polyurethanes. It is advantageouslyadditionally possible to dispense with the addition of water scavengers,or else to reduce the proportion of water scavengers, since the risk ofan unwanted blowing reaction falls with the selectivity of the catalystused for the gel reaction.

In a particularly advantageous embodiment of the invention, themetal-siloxane-silanol(ate) compound(s) are used in the production ofunfoamed polyurethanes, especially in the production of elastomers orthermosets. In one aspect, the invention thus relates to the use of atleast one metal-siloxane-silanol(ate) compound, especially a mononuclearmetallized silsesquioxane such as TiPOSS or SnPOSS, for the productionof unfoamed polyurethanes, especially for the production of elastomersor encapsulating compounds

In the context of the invention, “unfoamed polyurethane” is understoodto mean a polyurethane (also “polyurethane material”) having a densityof ≥800 kg/m³. Unfoamed polyurethanes are, for example, elastomers andthermosets. These may be encapsulating compounds or casting systems.

In a preferred embodiment, the unfoamed polyurethane produced/produciblein accordance with the invention has a density in the range of ≥800 to2000 kg/m³, preferably in the range from 950 to 1750 kg/m³, morepreferably in the range from 980 to 1650 kg/m³, most preferably in therange from 990 to 1600 kg/m³.

“Density” indicates the ratio of mass to volume of a material—i.e. thequotient of the mass m of a material and its volume V. According to theinvention, the density of unfoamed polyurethane, especially ofelastomers and encapsulating compounds, and foamed polyurethane,especially flexible and rigid foams, is determined according to DIN ENISO 845:2009-10.

The unfoamed polyurethanes producible in accordance with the invention,preferably with the densities as described above, have advantageoushardnesses. These can be classified and defined with the Shorehardnesses known to the person skilled in the art (see the definitionsand methods for the purpose below). Advantageously, the unfoamedpolyurethanes have the following hardnesses:

-   -   Shore 00 hardness in the range of 40-100, preferably in the        range from 45 to 95, preferably in the range from 50 to 90, more        preferably in the range from 55 to 85, and/or    -   Shore A hardness in the range of 0-100, preferably in the range        from 5 to 95, preferably in the range from 10 to 90, more        preferably in the range from 15 to 85, and/or    -   Shore D hardness in the range of 0-100, preferably in the range        from 5 to 95, preferably in the range from 10 to 90, more        preferably in the range from 15 to 85.

“Shore hardness” is a material index, for example for elastomers orplastics. It is directly related to the penetration depth of a body intothe material to be tested, and hence is a measure of the hardnessthereof. The penetration body (indenter) used is a spring-loaded stylusmade of hardened steel. In these methods, the respective indenter ispushed into the test specimen with a spring force. The penetration depthis thus a measure of the Shore hardness. The method of testing variesaccording to the force and sample head and can be expressed inter aliain the Shore hardnesses Shore 00, Shore A and Shore D. According to theinvention, the Shore hardnesses, whether Shore 00, Shore A or Shore Dhardness, are determined according to standard ASTM D2240-15.

As set out, it is possible in accordance with the invention preferablyto produce unfoamed polyurethanes, especially elastomers and thermosets,for example encapsulating compounds and/or casting systems.

Elastomers are generally notable for their fixed but elasticallydeformable tactile properties. Elastomers deform under tensile andcompressive stress, but return to their original, undeformed shape afterthe respective stress. Elastomers find use, inter alia, as material fortyres, rubber bands, gasket rings, etc.

Encapsulating compounds, especially polyurethane encapsulatingcompounds, are used in the specialist field for potting or encapsulatingcomponents and devices, inter alia. Their good flexibility, even at lowtemperatures, excellent water resistance and wide range of possiblecuring options make encapsulating compounds composed of polyurethaneideal for sensitive components and/or complex geometries. According tothe invention, Shore 00/ND hardnesses and densities for encapsulatingcompounds are within the abovementioned ranges for casting systems.

Casting systems, on account of their high thermal and chemicalstability, are used predominantly in adhesive and sealant systems.Casting systems are non-foaming 2-component encapsulating compoundsbased on polyurethane that have a low level of or are free of solvent.

According to the invention, in one embodiment, preference is given toproducing filled casting systems. These may preferably have a fillercontent of 5% to 70%, Shore A or Shore D hardnesses of 90, and densitiesbetween 1.1 and 1.8 g/cm³. Unfilled casting systems (filler content=0%)preferably have a Shore A hardness of 10, a Shore D hardness of 90, anda density of 0.85 to 1.2 g/cm³.

In a further aspect of the invention, the metal-siloxane-silanol(ate)compound is advantageously used in the production of foamedpolyurethanes. The polyurethanes thus produced preferably haveadvantageous tensile strengths. Thus, the inventors, in comparativeexperiments with conventional catalysts according to Example II(GF1-GF15) and (RF1-RF2) found, that foamed polyurethanes with elevatedtensile strengths are producible using TiPOSS. In this aspect of theinvention, therefore, at least one metal-siloxane-silanol(ate) compound,especially at least one mononuclear metallized silsesquioxane such asTiPOSS or SnPOSS, is used for the production of foamed polyurethaneshaving elevated strengths, especially flexible and/or rigid foams.

In the context of the invention, “foamed polyurethane” refers to apolyurethane having a density of ≤800 kg/m³. In the production of foamedpolyurethanes, a blowing catalyst is optionally used in addition to thegel catalyst. In the production of foamed polyurethanes, the blowingagent comes either from the reaction (in situ) or from an externalsource (external gas supply, for example by a gas cartridge).

“Blowing agent” is a gaseous substance, or substance that releases agas, or substance composition which is added to a composition in orderto generate pores therein in the course of further processing. The useof blowing agents thus serves to impart a desired porosity to adifferent material or to reduce material density. A blowing agent may beformed in situ, for example by reaction of two substances, as in theblowing reaction by the reaction of an isocyanate-containing componentwith water (here: gaseous CO₂↑), or alternatively be supplied to thematerial from an external source. One example of the latter variant isthe supply of a gas, for example CO₂, N₂, Ar, H₂, O₂ or other gases ormixtures thereof, for example by means of gas cartridges and/orintroduction pipes or nozzles. A “blowing gas” is a blowing agent.

In this inventive use of the metal-siloxane-silanol(ate) compound, ithas been found that the foams produced in this way, especially flexibleand rigid foams, feature a homogeneous pore structure. The rigid foamsalso show a fine-cell or fine-pore distribution of the cavities in thematerial. This results in advantageous properties with regard to thermalconductivity. The invention therefore also relates, in one aspect, tothe production of foams for the provision of materials for thermalinsulation.

In a preferred embodiment of this inventive use of themetal-siloxane-silanol(ate) compound, it is preferably possible toproduce foamed polyurethanes of a density in the range from 100 to 900kg/m³, preferably in the range from 150 to 850 kg/m³, more preferably inthe range from 200 to 750 kg/m³, most preferably in the range from 200to 650 kg/m³.

It is possible with preference in accordance with the invention toobtain foamed polyurethanes having the following Shore hardnesses(definitions as above):

-   -   Shore 00 hardness in the range of 10-100, preferably in the        range from 10 to 90, preferably in the range from 20 to 80, more        preferably in the range from 35 to 75, and/or    -   Shore A hardness in the range of 0-100, preferably in the range        from 20 to 95, preferably in the range from 20 to 60, more        preferably in the range from 20 to 50, and/or    -   Shore D hardness in the range of 0-90, preferably in the range        from 10 to 90, preferably in the range from 20 to 80, more        preferably in the range from 35 to 75.

In a further aspect of the invention, the metal-siloxane-silanol(ate)compound is used in accordance with the invention especially forproduction of flexible foams. Flexible foams typically have a longlifetime, good resilience and good deformability. The density offlexible foams produced/producible in accordance with the inventionvaries between about 5 and 650 kg/m³, and that of slabstock foamsbetween 25 and 300 kg/m³.

In a particularly advantageous embodiment, according to the invention, aflexible foam having a Shore A hardness of ≥20 is produced. Especiallypreferred is the production of a flexible foam having a Shore A hardnessbetween 20 and 100, preferably between 20 and 60, more preferablybetween 20 and 50.

The flexible foams producible/produced in accordance with the inventionadvantageously have a tensile strength of ≥200 kPa. Especially preferredare flexible foams having a tensile strength between 200 and 350 kPa.Tensile strength and methods for determination thereof are definedbelow. They are known to the person skilled in the art.

In a particularly preferred embodiment of the invention, the flexiblefoams have a Shore A hardness between 20 and 50 and a tensile strengthbetween 200 and 350 kPa.

In a further advantageous embodiment, the metal-siloxane-silanol(ate)compound is used as catalyst for the production of rigid polyurethanefoams. Rigid foams generally feature a long lifetime, high shape anddimensional stability, and low thermal conductivities and low moldcavity pressures.

The inventive use of the metal-siloxane-silanol(ate) compound canespecially be used for production of rigid foams of density in the rangefrom 25 to 900 kg/m³. These foams preferably serve for thermalinsulation, for example in buildings, cooling equipment, heat and coldreservoirs, and some pipe systems (outer plastic composite pipe,flexible composite pipes). In this aspect, the inventive use thereforerelates to the production of insulation material.

In a preferred embodiment, the rigid foams have a Shore D hardness of≥10. Further preferably, Shore D hardness is between 15 and 100,preferably between 20 and 95, most preferably between 25 and 90.

In a further preferred embodiment, the rigid foams have a tensilestrength of ≥100 kPa, especially of 200 to 2000 kPa. The tensilestrength here is preferably ≥350 kPa.

It is most preferable to use the metal-siloxane-silanol(ate) compoundfor production of rigid foams of Shore D hardness between 25 and 90 andtensile strength between 350 and 2000 kPa.

“Tensile strength” is a strength index of a material. Tensile strengthdescribes the maximum mechanical tension that a material withstands.When the tensile strength is exceeded, the material breaks, tears orshatters. The dimension for tensile strength is force per unit area—theunits of measurement used are N/mm² or kPa/MPa. The test methods fordetermination of tensile strength and elongation at break are known tothe person skilled in the art. For flexible foams they can preferably beconducted according to DIN EN ISO 1798:2008-04, and for rigid foamsaccording to ISO 1926:2009-12.

In a particularly preferred embodiment, at least onemetal-siloxane-silanol(ate) compound is used for selective catalysis ofthe gel reaction in a two-component (2K) system. The (2K) systemcomprises a component A and a component B. Component A comprises atleast one hydroxy-functionalized polymer. Component B comprises at leastone compound having one or more isocyanate groups. Themetal-siloxane-silanol(ate) compound(s) may be formulated or included inone of the two components or in both components. Preference is given toformulating or including the metal-siloxane-silanol(ate) compound(s)with component A.

It additionally follows for the gel reaction from the selectivity of themetal-siloxane-silanol(ate) compounds that have been found by theinventors that the metal-siloxane-silanol(ate) compounds make itpossible to reduce the level of or dispense with water scavengers thatare added additionally. This in turn results in the conservation ofresources and lowering of the costs through saving of material. The useaccording to the invention further permits the use of raw materials thatdo not have to undergo any particular or additional drying. Furthermore,the use according to the invention makes the mixtures in question morestorage-stable.

The use of at least one metal-siloxane-silanol(ate) compound forselective catalysis of the gel reaction in a system for the productionof polyurethanes results in a reduction in unwanted or uncontrolled sidereactions (for example the blowing reaction). The product yield isaccordingly greater in the use according to the invention withoutdisruptive side reactions.

Surprisingly, reaction mixtures with inventive use of the blowingcatalyst do not require any further or additional catalysts for curingin production of polyurethanes. The use of the gel catalyst according tothe invention therefore makes it possible to reduce the level of orentirely dispense with tin-containing (gel) catalysts and/or aminecatalysts.

In addition to dispensing with water scavengers and further catalysts,it is also possible to use a lower level of isocyanate-containingcompounds, since these, by virtue of the use according to the invention,no longer have to be added in an elevated excess (beyond the reactionstoichiometry required). In the prior art, they occasionally also serveas water scavengers and to maintain the stability and reactivity ofreaction mixtures for production of polyurethanes.

In a further aspect of the invention, it is thus possible to generallyfurther reduce the use of substances harmful to health and to makeemployment more user-friendly for the end user.

According to the invention, “water scavengers” are compounds orsubstances that are added to a mixture of constituents with the aim ofthemselves reacting with/depleting water or binding water. The additionof water scavengers in the main application avoids the unwanted presenceof water, for example on account of problematic or unwanted reactions ofwater with further mixture constituents.

The high selectivity coupled with a high catalytic activity of themetal-siloxane-silanol(ate) compounds in use for selective catalysis ofthe gel reaction for the production of polyurethanes (PU) also allowsthe catalyst input to be reduced overall. According to the reactants andreaction regime used for production of polyurethane materials, theamounts of catalyst required may be in the range from 10 to 75 000 ppm,preferably in the range from 15 to 10 000 ppm or in the range from 20 to5000 ppm.

In the context of the invention, “polyurethanes” are also polyurethanematerials, polyurethane substances or polyurethane systems, or polymerscomprising urethane linkages. Alternatively, the abbreviation “PU” islikewise used for polyurethane. In a generally customary manner and inaccordance with the invention, polyurethanes are divided into unfoamedand foamed polyurethanes.

According to the invention, “urethane linkage” or else “urethane bond”is used for the urethane units or groups that form in the production ofpolyurethanes. The urethane unit or group itself is shown here in boldtype: R—NH—CO—OR′. This can form, for example, through a reaction orlinkage of an isocyanate group (—N═C═O) in an isocyanate-containingcompound with a hydroxyl group (—OH) in a hydroxy-functionalized polymeror polyol.

According to the invention, isocyanate-reactive compounds are those thatcan react with an isocyanate. These compounds may have one or more NH,OH or SH functions.

The isocyanate-reactive compounds especially include the class of thehydroxy-functional compounds. Polyols are hydroxy-functional compounds,especially hydroxy-functional polymers. Suitable polyols for thepreparation of polyurethane polymers are especially polyether polyols,polyester polyols and polycarbonate polyols, and mixtures of thesepolyols.

“Polyethers” are a class of polymers. They are long-chain compoundscomprising at least two identical or different ether groups. Accordingto the invention, polyethers also include those where the polymericether groups are interrupted by another group (for example bycopolymerized/incorporated isocyanates or further polymer or oligomericunits of a different monomer origin).

“Polymers” are chemical compounds composed of chain or branchedmolecules (macromolecules) but in turn consist of a number ofidentical/equivalent or else different units, called the monomers.Polymers also include oligomers. Oligomers are polymers having a smallernumber of units. Unless explicitly defined differently, oligomers areincluded in the concept of polymers in accordance with the invention.Polymers may occur as homopolymers (=consisting only of one monomerunit), copolymers (=consisting of two or more monomer units) or as apolymer mixture (=polymer alloy, polymer blends, i.e. mixtures ofdifferent polymers and copolymers).

Suitable polyether polyols, also called polyoxyalkylene polyols oroligoetherols, are especially those that are polymerization products ofethylene oxide, 1,2-propylene oxide, 1,2- or 2,3-butylene oxide,oxetane, tetrahydrofuran or mixtures thereof, optionally polymerizedwith the aid of a starter molecule having two or more

active hydrogen atoms, for example water, ammonia or compounds havingmultiple OH or NH groups, for example ethane-1,2-diol, propane-1,2- and-1,3-diol, neopentyl glycol, diethylene glycol, triethylene glycol, theisomeric dipropylene glycols and tripropylene glycols, the isomericbutanediols, pentanediols, hexanediols, heptanediols, octanediols,nonanediols, decanediols, undecanediols, cyclohexane-1,3- and-1,4-dimethanol, bisphenol A, hydrogenated bisphenol A,1,1,1-trimethylolethane, 1,1,1-trimethylolpropane, pentaerythritol,sorbitol, sugar, dipentaerythritol, glycerol, aniline, and mixtures ofthe compounds mentioned.

It is possible to use either polyoxyalkylene polyols having a low degreeof unsaturation (measured in accordance with ASTM D-2849-69 andexpressed in milliequivalents of unsaturation per gram of polyol(mEq/g)), produced for example using so-called double metal cyanidecomplex catalysts (DMC catalysts), or polyoxyalkylene polyols having arelatively high degree of unsaturation, produced for example usinganionic catalysts such as NaOH, KOH, CsOH or alkali metal alkoxides.Polyoxyethylene polyols and polyoxypropylene polyols are particularlysuitable, especially polyoxyethylene diols, polyoxypropylene diols,polyoxyethylene triols, and polyoxypropylene triols.

Especially suitable are polyoxyalkylene diols or polyoxyalkylene triolshaving a degree of unsaturation lower than 0.02 mEq/g and having amolecular weight within a range from 1000 g/mol to 30 000 g/mol, as arepolyoxyethylene diols, polyoxyethylene triols, polyoxypropylene diols,and polyoxypropylene triols having a molecular weight of 200 to 20 000g/mol. Likewise particularly suitable are so-called ethyleneoxide-terminated (“EO-endcapped”, ethylene oxide-endcapped)polyoxypropylene polyols. The latter are special polyoxypropylenepolyoxyethylene polyols that are obtained for example when purepolyoxypropylene polyols, in particular polyoxypropylene diols andtriols, are at the end of the polypropoxylation reaction furtheralkoxylated with ethylene oxide and thus have primary hydroxyl groups.Preference in this case is given to polyoxypropylene polyoxyethylenediols and polyoxypropylene polyoxyethylene triols. Also suitable arehydroxyl-terminated polybutadiene polyols, for example those produced bypolymerization of 1,3-butadiene and allyl alcohol or by oxidation ofpolybutadiene and also the hydrogenation products thereof. Also suitableare styrene-acrylonitrile grafted polyether polyols such as thosecommercially available for example under the trade name Lupranol® fromElastogran GmbH, Germany.

Suitable polyester polyols include in particular polyesters that bear atleast two hydroxyl groups and are produced by known processes, inparticular polycondensation of hydroxycarboxylic acids orpolycondensation of aliphatic and/or aromatic polycarboxylic acids withdihydric or polyhydric alcohols.

Especially suitable are polyester polyols produced from dihydric totrihydric alcohols such as ethane-1,2-diol, diethylene glycol,propane-1,2-diol, dipropylene glycol, butane-1,4-diol, pentane-1,5-diol,hexane-1,6-diol, neopentyl glycol, glycerol, 1,1,1-trimethylolpropane ormixtures of the abovementioned alcohols with organic dicarboxylic acidsor the anhydrides or esters thereof, for example succinic acid, glutaricacid, adipic acid, trimethyladipic acid, suberic acid, azelaic acid,sebacic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid,dimer fatty acid, phthalic acid, phthalic anhydride, isophthalic acid,terephthalic acid, dimethyl terephthalate, hexahydrophthalic acid,trimellitic acid and trimellitic anhydride or mixtures of theabovementioned acids, as are polyester polyols formed from lactones suchas ε-caprolactone. Particularly suitable are polyester diols, inparticular those produced from adipic acid, azelaic acid, sebacic acid,dodecanedicarboxylic acid, dimer fatty acid, phthalic acid, isophthalicacid and terephthalic acid as the dicarboxylic acid or from lactonessuch as ε-caprolactone and from ethylene glycol, diethylene glycol,neopentyl glycol, butane-1,4-diol, hexane-1,6-diol, dimer fatty aciddiol, and cyclohexane-1,4-dimethanol as the dihydric alcohol.

Suitable polycarbonate polyols include in particular those obtainable byreaction for example of the abovementioned alcohols used to form thepolyester polyols with dialkyl carbonates such as dimethyl carbonate,diaryl carbonates such as diphenyl carbonate, or phosgene. Polycarbonatediols, in particular amorphous polycarbonate diols, are particularlysuitable. In addition, polycarbonate diols or polyether polycarbonatediols may be obtainable via polymerization of propylene oxide with CO₂.

Further suitable polyols are poly(meth)acrylate polyols.

Also suitable are polyhydroxy-functional fats and oils, for examplenatural fats and oils, in particular castor oil, or so-calledoleochemical polyols obtained by chemical modification of natural fatsand oils, the epoxy polyesters or epoxy polyethers obtained for exampleby epoxidation of unsaturated oils and subsequent ring opening withcarboxylic acids or alcohols respectively, or polyols obtained byhydroformylation and hydrogenation of unsaturated oils. Also suitableare polyols obtained from natural fats and oils by degradation processessuch as alcoholysis or ozonolysis and subsequent chemical linking, forexample by transesterification or dimerization, of the thus obtaineddegradation products or derivatives thereof. Suitable breakdown productsof natural fats and oils are in particular fatty acids and fattyalcohols and also fatty acid esters, in particular the methyl esters(FAME), which can be derivatized to hydroxy fatty acid esters, forexample by hydroformylation and hydrogenation.

Likewise suitable are, in addition, polyhydrocarbon polyols, alsoreferred to as oligohydrocarbonols, for example polyhydroxy-functionalethylene-propylene, ethylene-butylene or ethylene-propylene-dienecopolymers, for example those produced by Kraton Polymers, USA, orpolyhydroxy-functional copolymers of dienes, such as 1,3-butadiene ordiene mixtures, and vinyl monomers such as styrene, acrylonitrile orisobutylene, or polyhydroxy-functional polybutadiene polyols, forexample those which are produced by copolymerization of 1,3-butadieneand allyl alcohol and which may also be hydrogenated. Also suitable arepolyhydroxy-functional acrylonitrile/butadiene copolymers, such as thosethat can be produced for example from epoxides or amino alcohols andcarboxyl-terminated acrylonitrile/butadiene copolymers that arecommercially available under the Hypro® CTBN name from EmeraldPerformance Materials, LLC, USA.

These likewise particularly preferred polyols may have an averagemolecular weight of 250 to 40 000 g/mol, especially of 1000 to 30 000g/mol, and an average OH functionality in the range from 1.6 to 6.

Particularly suitable polyols are polyester polyols and polyetherpolyols, in particular polyoxyethylene polyol, polyoxypropylene polyol,and polyoxypropylene polyoxyethylene polyol, preferably polyoxyethylenediol, polyoxypropylene diol, polyoxyethylene triol, polyoxypropylenetriol, polyoxypropylene polyoxyethylene diol, and polyoxypropylenepolyoxyethylene triol.

In addition to these polyols mentioned, it is also possible to use smallamounts of low molecular weight di- or polyhydric alcohols, for exampleethane-1,2-diol, propane-1,2- and -1,3-diol, neopentyl glycol,diethylene glycol, triethylene glycol, the isomeric dipropylene glycolsand tripropylene glycols, the isomeric butanediols, pentanediols,hexanediols, heptanediols, octanediols, nonanediols, decanediols,undecanediols, cyclohexane-1,3- and -1,4-dimethanol, hydrogenatedbisphenol A, dimeric fatty alcohols, 1,1,1-trimethylolethane,1,1,1-trimethylolpropane, glycerol, pentaerythritol, sugar alcohols suchas xylitol, sorbitol or mannitol, sugars such as sucrose, other higherpolyhydric alcohols, low molecular weight alkoxylation products of theaforementioned di- and polyhydric alcohols, and mixtures of theaforementioned alcohols in the use of the gel catalyst according to theinvention in the production of polyurethanes, especially of unfoamedpolyurethanes and/or in a two-component (2K) system according to theinvention.

Isocyanate-containing compounds (Iso) have at least one NCO group(=isocyanate group). A distinction may be made between themonoisocyanates (z=1) and the di- and polyisocyanates (z=≥2). The NCOgroups may react, for example, with alcohols to give urethanes or withamines to give urea derivatives. The isocyanate-containing compounds ofthe invention may be described by the general formula (VI)

R^(x)

N═C═O)_(z)  (VI)

where

-   -   R^(x) is a carbon-containing group, preferably at least one        aromatic or aliphatic group or mixtures thereof, more preferably        an optionally substituted straight-chain or branched C1- to        C20-alkyl group, an optionally substituted straight-chain or        branched C2- to C20-alkenyl group or an optionally substituted        straight-chain or branched C2- to C20-alkynyl group, an        optionally substituted C4- to C14-cycloalkyl group or an        optionally substituted C4- to C14-aryl group, most preferably        diphenylmethane, toluene, dicyclohexylmethane, hexane or        methyl-3,5,5-trimethylcyclohexyl,    -   z is at least 1, preferably at least 1, 2 or 3, more preferably        1, 2 or 3.

The term “metal-siloxane-silanol(ate)” refers to all metal-siloxanecompounds that contain either one or more silanol and/or silanolategroups. In one embodiment of the invention, it is likewise possible thatthere are exclusively metal-siloxane-silanolates. If no specificdifferentiation is made between these different configurations, allcombinations are included. The metal-siloxane-silanol(ate) compounds(=metal-siloxane-silanol/silanolate compounds) just described are alsoreferred to hereinafter as oligomeric metallosilsesquioxanes, “POMS”,metal silsesquioxanes or metallized silsesquioxanes. The terms are usedinterchangeably hereinafter.

“Alkoxy” refers to an alkyl group joined via an oxygen atom to the maincarbon chain or the main skeleton of the compound.

Unless stated otherwise, N especially denotes nitrogen. In addition, Oespecially denotes oxygen, unless stated otherwise. S especially denotessulfur, unless stated otherwise. P especially denotes phosphorus, unlessstated otherwise. C especially denotes carbon, unless stated otherwise.H especially denotes hydrogen, unless stated otherwise. Si especiallydenotes silicon, unless stated otherwise.

“Optionally substituted” means that hydrogen atoms in the correspondinggroup or in the corresponding radical may be replaced by substituents.Substituents may especially be selected from the group consisting of C1-to C4-alkyl, methyl, ethyl, propyl, butyl, phenyl, benzyl, halogen,fluorine, chlorine, bromine, iodine, hydroxy, amino, alkylamino,dialkylamino, C1- to C4-alkoxy, phenoxy, benzyloxy, cyano, nitro, andthio. If a group is referred to as optionally substituted, it ispossible for 0 to 50, especially 0 to 20, hydrogen atoms of the group tobe replaced by substituents. If a group is substituted, at least onehydrogen atom is replaced by a substituent.

The term “alkyl group” is to be understood as meaning a saturatedhydrocarbon chain. Alkyl groups especially have the general formula—C_(n)H_(2n+1). The term “C1- to C16-alkyl group” especially denotes asaturated hydrocarbyl chain having 1 to 16 carbon atoms in the chain.Examples of C1- to C16-alkyl groups are methyl, ethyl, propyl, butyl,isopropyl, isobutyl, sec butyl, tert-butyl, n-pentyl and ethylhexyl.Correspondingly, a “C1- to C8-alkyl group” especially denotes asaturated hydrocarbyl chain having 1 to 8 carbon atoms in the chain.Alkyl groups may especially also be substituted even if this is notstated specifically.

“Straight-chain alkyl groups” denote alkyl groups containing nobranches. Examples of straight-chain alkyl groups are methyl, ethyl,n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl and n-octyl.

“Branched alkyl groups” denote alkyl groups that are not straight-chain,i.e. in which the hydrocarbyl chain especially has a fork. Examples ofbranched alkyl groups are isopropyl, isobutyl, sec-butyl, tert-butyl,sec-pentyl, 3-pentyl, 2-methylbutyl, isopentyl, 3-methylbut-2-yl,2-methylbut-2-yl, neopentyl, ethylhexyl, and 2-ethylhexyl.

“Alkenyl groups” describe hydrocarbon chains containing at least onedouble bond along the chain. For example an alkenyl group having adouble bond in particular has the general formula —C_(n)H_(2n−1).However, alkenyl groups may also have more than one double bond. Theterm “C2-to C16-alkenyl group” especially denotes a hydrocarbyl chainhaving 2 to 16 carbon atoms in the chain. The number of hydrogen atomsvaries according to the number of double bonds in the alkenyl group.Examples of alkenyl groups are vinyl-, allyl-, 2-butenyl- and2-hexenyl-.

“Straight-chain alkenyl groups” denote alkenyl groups containing nobranches. Examples of straight-chain alkenyl groups are vinyl, allyl,n-2-butenyl and n-2-hexenyl.

“Branched alkenyl groups” denote alkenyl groups that are notstraight-chain, i.e. in which the hydrocarbyl chain especially has afork. Examples of branched alkenyl groups are 2-methyl-2-propenyl,2-methyl-2-butenyl and 2-ethyl-2-pentenyl.

“Aryl groups” denote monocyclic (for example phenyl), bicyclic (forexample indenyl, naphthalenyl, tetrahydronapthyl or tetrahydroindenyl)and tricyclic (for example fluorenyl, tetrahydrofluorenyl, anthracenylor tetrahydroanthracenyl) ring systems in which the monocyclic ringsystem or at least one of the rings in a bicyclic or tricyclic ringsystem is aromatic. More particularly, a C4- to C14-aryl group denotesan aryl group having 4 to 14 carbon atoms. Aryl groups may especiallyalso be substituted even if this is not stated specifically.

In one embodiment of the invention, a system according to the invention,especially a two-component (2K) system, comprises at least onemetal-siloxane-silanol(ate) compound, where themetal-siloxane-silanol(ate) compound, is present with a proportion byweight in the range from 0.001% to 5%, preferably in the range from0.002% to 1%, more preferably in the range from 0.003% to 0.5%, based ineach case on the total weight of the reaction mixture. The two-component(2K) systems according to the invention containmetal-siloxane-silanol(ate) compounds in molar concentrations in therange from 0.00001 to 0.06 mol/kg, preferably in the range from 0.00002to 0.01 mol/kg, more preferably in the range from 0.00003 to 0.06mol/kg, based in each case on the total weight of the reaction mixture.

According to the invention, “reaction mixture” is understood to mean theoverall composition of a system, especially of a two-component (2K)system, i.e. the sum total of components A and B, and also gel catalystand optionally further catalysts, auxiliaries and constituents. Theresult of a reaction mixture on completion of reaction is apolyurethane.

In one embodiment of the present invention, themetal-siloxane-silanol(ate) compound may take the form of a monomer,oligomer and/or polymer for production of polyurethanes, the transitionfrom oligomers to polymers being fluid according to the generaldefinition.

The metal(s) is/are preferably present terminally and/or within thechain in the oligomeric and/or polymeric metal-siloxane-silanol(ate)compound.

In the use according to the invention for production of polyurethanes,preferably of unfoamed polyurethanes, flexible foams or rigid foamsand/or in the two-component (2K) system according to the invention, thecatenated metal-siloxane-silanol(ate) compound is linear, branchedand/or a cage.

In a preferred use according to the invention for production ofpolyurethanes, preferably of unfoamed polyurethanes, flexible foams orrigid foams and/or in the two-component (2K) system according to theinvention, the catenated metal-siloxane-silanol(ate) compound has a cagestructure.

A “cage” or an oligomeric or polymeric “cage structure” for the purposesof the present invention is a three-dimensional arrangement of thecatenated metal-siloxane-silanol(ate) compound, wherein individual atomsin the chain form the vertices of a multifaceted base structure of thecompound. In this case, the mutually linked atoms form at least twosurfaces, giving rise to a common intersection. In one embodiment of theinvention, for example, a cubic base structure of the compound isformed. A one-cage structure or else a cage structure in singular form,i.e. a compound that has an isolated cage, is the structure (IVc).Compounds having multiple cages within the compound may be described bythe compounds (I) and (Ia) to (Id). According to the invention, a cagemay be “open” or else “closed”, depending on whether all vertices arebonded, joined or coordinated so as to form a closed cage structure. Oneexample of a closed cage is the structures (II), (IV), (IVb), (IVc).

According to the invention, the term “-nuclear” gives the nuclearity ofa compound, how many metal atoms are present therein. A mononuclearcompound has one metal atom, whereas a dinuclear compound has two metalatoms within a compound. The metals may be bonded directly to oneanother or linked via their substituents. One example of a mononuclearcompound according to the invention is, for example, the structures(IV), (IVb), (IVc), (Ia), (Ib) or (Ic); a dinuclear compound isrepresented by structure (Id).

A mononuclear one-cage structure is represented by themetal-siloxane-silanol(ate) compounds (IV), (IVb) and (IVc). Mononucleartwo-cage structures are, for example, the structures (Ia), (Ib) or (Ic).

The metal-siloxane-silanol(ate) compound in the use according to theinvention for selective catalysis of the gel reaction for the productionof polyurethanes, preferably of unfoamed polyurethanes, flexible foamsor rigid foams and/or in the two-component (2K) system according to theinvention, preferably comprises an oligomeric metal silsesquioxane.

More particularly, the metal-siloxane-silanol(ate) compound in the useaccording to the invention for selective catalysis of the gel reactionfor the production of polyurethanes, preferably of unfoamedpolyurethanes, flexible foams or rigid foams and/or in the two-component(2K) system according to the invention, comprises a polyhedral metalsilsesquioxane.

In one embodiment, the metal-siloxane-silanol(ate) compound in the useaccording to the invention for selective catalysis of the gel reactionfor the production of polyurethanes, preferably of unfoamedpolyurethanes, flexible foams or rigid foams and/or in the two-component(2K) system according to the invention has the general formulaR*_(q)Si_(r)O_(s)M_(t) where each R* is independently selected from thegroup consisting of optionally substituted C1- to C20-alkyl, optionallysubstituted C3- to C8-cycloalkyl, optionally substituted C2- toC20-alkenyl, optionally substituted C5- to C10-aryl, —OH and —O—(C1- toC10-alkyl), each M is independently selected from the group consistingof s- and p-block metals, d- and f-block transition metals, lanthanideand actinide metals and semimetals, especially from the group consistingof metals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metalsfrom main group 1, 2, 3, 4 and 5, preferably from the group consistingof Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especiallypreferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn andBi,

q is an integer from 4 to 19,r is an integer from 4 to 10,s is an integer from 8 to 30, andt is an integer from 1 to 8.

In a further embodiment, the metal-siloxane-silanol(ate) compound in theuse according to the invention for selective catalysis of the gelreaction for the production of polyurethanes, preferably of unfoamedpolyurethanes, flexible foams or rigid foams and/or in the two-component(2K) system according to the invention has the general formula R^(#)₄Si₄O₁₁Y₂Q₂X₄Z₃ where each X is independently selected from the groupconsisting of Si, M¹, -M³L¹ _(Δ), M³, or —Si(R⁶)—O-M³L¹ _(Δ), where M¹and M³ are independently selected from the group consisting of s- andp-block metals, d- and f-block transition metals, lanthanide andactinide metals and semimetals, especially from the group consisting ofmetals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals frommain group 1, 2, 3, 4 and 5, preferably from the group consisting of Na,Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especiallypreferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn andBi, and

where L¹ is selected from the group consisting of —OH and —O—(C1- toC10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), orwhere L¹ is selected from the group consisting of —OH, —O-methyl,—O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl,and where R⁸ is selected from the group consisting of optionallysubstituted C1- to C20-alkyl, optionally substituted C3- toC8-cycloalkyl, optionally substituted C2- to C20-alkenyl and optionallysubstituted C5- to C10-aryl;each Z is independently selected from the group consisting of L², R⁵, R⁶and R⁷, where L² is selected from the group consisting of —OH and—O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- toC6-alkyl), or where L² is selected from the group consisting of —OH, —O—methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and—O-isobutyl;each R^(#), R⁵, R⁶ and R⁷ is independently selected from the groupconsisting of optionally substituted C1- to C20-alkyl, optionallysubstituted C3- to C8-cycloalkyl, optionally substituted C2- toC20-alkenyl and optionally substituted C5- to C10-aryl; each Y isindependently —O-M²-L³ _(Δ), or two Y are associated and together are—O-M²(L³ _(Δ))-O— or —O—, where L³ is selected from the group consistingof —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or—O—(C1- to C6-alkyl), or where L³ is selected from the group consistingof —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl,—O-isopropyl, and —O-isobutyl, and each M² is independently selectedfrom the group consisting of s- and p-block metals, d- and f-blocktransition metals, lanthanide and actinide metals and semimetals,especially from the group consisting of metals from transition group 1,2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5,preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V,Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the groupconsisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,each Q is independently H, M⁴L⁴ _(Δ), —SiR⁸, -M³L¹ _(Δ), a single bondjoined to M³ of X or a single bond joined to the Si atom of the—Si(R⁸)—O-M³L¹ _(Δ) radical, where M³, R⁸ and L¹ are as defined for X,where M⁴ is selected from the group consisting of s- and p-block metals,d- and f-block transition metals, lanthanide and actinide metals andsemimetals, especially from the group consisting of metals fromtransition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc,Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably fromthe group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, and where L⁴is selected from the group consisting of —OH and —O—(C1- to C10-alkyl),especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L⁴ isselected from the group consisting of —OH, —O-methyl, —O-ethyl,—O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl,with the proviso that at least one X is M³, -M³L¹ _(Δ) or —Si(R⁸)—O-M³L¹_(Δ).

It is known to the person skilled in the art that the number (A) ofpossible ligands for L¹ _(Δ), L² _(Δ), L³ _(Δ), L⁴ _(Δ) results directlyfrom the number of free valences of the metal atom used, where thevalence number describes the valency of the metal.

In a further embodiment, the metal-siloxane-silanol(ate) compound in theuse according to the invention for selective catalysis of the gelreaction for the production of polyurethanes, preferably of unfoamedpolyurethanes, flexible foams or rigid foams and/or in the two-component(2K) system according to the invention has the general formula(Y_(0.25)R^(#)SiO_(1.25))₄(Z_(0.75)Y_(0.25)XO)₄(OQ)₂ where each X isindependently selected from the group consisting of Si, M¹, -M³L¹ _(Δ),M³, or —Si(R⁸)—O-M³L¹ _(Δ), where M¹ and M³ are independently selectedfrom the group consisting of s- and p-block metals, d- and f-blocktransition metals, lanthanide and actinide metals and semimetals,especially from the group consisting of metals from transition group 1,2, 3, 4, 5, 8, 10 and 11 and metals from main group 1, 2, 3, 4 and 5,preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V,Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the groupconsisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, and where L¹ is selectedfrom the group consisting of —OH and —O—(C1- to C10-alkyl), especially—O—(C1-to C8-alkyl) or —O—(C1- to C6-alkyl), or where L¹ is selectedfrom the group consisting of —OH, —O-methyl, —O-ethyl, —O-propyl,—O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and where R⁸ isselected from the group consisting of optionally substituted C1- toC20-alkyl, optionally substituted C3- to C6-cycloalkyl, optionallysubstituted C2- to C20-alkenyl and optionally substituted C6- toC10-aryl;

each Z is independently selected from the group consisting of L², R⁵, R⁶and R⁷, where L² is selected from the group consisting of —OH and—O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- toC6-alkyl), or where L² is selected from the group consisting of —OH, —O—methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and—O-isobutyl;each R^(#), R⁵, R⁶ and R⁷ is independently selected from the groupconsisting of optionally substituted C1- to C20-alkyl, optionallysubstituted C3- to C6-cycloalkyl, optionally substituted C2- toC20-alkenyl and optionally substituted C6- to C10-aryl;each Y is independently —O-M²-L³ _(Δ), or two Y are associated andtogether are —O-M²(L³ _(Δ))-O— or —O—, where L³ is selected from thegroup consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- toC8-alkyl) or —O—(C1- to C6-alkyl), or where L³ is selected from thegroup consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl,—O-octyl, —O-isopropyl, and —O-isobutyl, and each M² is independentlyselected from the group consisting of s- and p-block metals, d- andf-block transition metals, lanthanide and actinide metals andsemimetals, especially from the group consisting of metals fromtransition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc,Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably fromthe group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,each Q is independently H, M⁴L⁴ _(Δ), —SiR⁸, -M³L¹ _(Δ), a single bondjoined to M³ of X or a single bond joined to the Si atom of the—Si(R⁸)—O-M³L¹ _(Δ) radical, where M³, R⁸ and L¹ are as defined for X,where M⁴ is selected from the group consisting of s- and p-block metals,d- and f-block transition metals, lanthanide and actinide metals andsemimetals, especially from the group consisting of metals fromtransition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc,Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably fromthe group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, and where L⁴is selected from the group consisting of —OH and —O—(C1- to C10-alkyl),especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L⁴ isselected from the group consisting of —OH, —O-methyl, —O-ethyl,—O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl,with the proviso that at least one X is M³, -M³L¹ _(Δ) or —Si(R⁸)—O-M³L¹_(Δ).

The metal-siloxane-silanol(ate) compound in the use according to theinvention for selective catalysis of the gel reaction for the productionof polyurethanes, preferably of unfoamed polyurethanes, flexible foamsor rigid foams and/or in the two-component (2K) system according to theinvention preferably has the general formulaSi₄O₉R¹R²R³R⁴X¹X²X³X⁴OQ¹OQ²Y¹Y²Z¹Z²Z³ where X¹, X² and X³ areindependently selected from Si and M¹, where M¹ is selected from thegroup consisting of s- and p-block metals, B- and f-block transitionmetals, lanthanide and actinide metals and semimetals, especially fromthe group consisting of metals from transition group 1, 2, 3, 4, 5, 8,10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably fromthe group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga,Sn and Bi; especially preferably from the group consisting of Zn, Ti,Zr, Hf, V, Fe, Sn and Bi,

Z¹, Z² and Z³ are independently selected from the group consisting ofL², R⁵, R⁶ and R⁷, where L² is selected from the group consisting of —OHand —O—(C1- to C10-alkyl), especially —O—(C1-to C8-alkyl) or —O—(C1- toC6-alkyl), or where L2 is selected from the group consisting of —OH,—O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and—O-isobutyl;R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are independently selected from the groupconsisting of optionally substituted C1- to C20-alkyl, optionallysubstituted C3- to C8-cycloalkyl, optionally substituted C2- toC20-alkenyl and optionally substituted C5- to C10-aryl;Y¹ and Y² are independently —O-M²-L³ _(Δ), or Y¹ and Y² are associatedand together are —O-M²(L³ _(Δ))-O— or —O—, where L³ is selected from thegroup consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- toC8-alkyl) or —O—(C1- to C6-alkyl), or where L³ is selected from thegroup consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl,—O-octyl, —O-isopropyl, and —O-isobutyl, and M² is selected from thegroup consisting of s- and p-block metals, d- and f-block transitionmetals, lanthanide and actinide metals and semimetals, especially fromthe group consisting of metals from transition group 1, 2, 3, 4, 5, 8,10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably fromthe group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga,Sn and Bi; especially preferably from the group consisting of Zn, Ti,Zr, Hf, V, Fe, Sn and Bi, andX⁴ is -M³L¹ _(Δ) or M³ and Q¹ and Q² are each H or a single bond joinedto M³, where L¹ is selected from the group consisting of —OH and —O—(C1-to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl),or where L¹ is selected from the group consisting of —OH, —O-methyl, —O—ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, andwhere M³ is selected from the group consisting of s- and p-block metals,d- and f-block transition metals, lanthanide and actinide metals andsemimetals, especially from the group consisting of metals fromtransition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc,Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably fromthe group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,orX⁴ is -M³L¹ _(Δ) and Q² is H or a single bond joined to M³ and Q¹ is H,M⁴L⁴ _(Δ) or —SiR⁸, where M⁴ is selected from the group consisting of s-and p-block metals, d- and f-block transition metals, lanthanide andactinide metals and semimetals, especially from the group consisting ofmetals from transition group 2, 3, 4, 5 and 8 and metals from main group1, 2, 3, 4 and 5, especially from the group consisting of Zn, Sc, Ti,Zr, Hf, V, Pt, Ga, Sn and Bi, where L⁴ is selected from the groupconsisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- toC8-alkyl) or —O—(C1- to C6-alkyl), or where L⁴ is selected from thegroup consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl,—O-octyl, —O-isopropyl, and —O-isobutyl, and where R⁸ is selected fromthe group consisting of optionally substituted C1- to C20-alkyl,optionally substituted C3- to C8-cycloalkyl, optionally substituted C2-to C20-alkenyl and optionally substituted C5- to C10-aryl,orX⁴, Q¹ and Q² are independently -M³L¹ _(Δ),orX⁴ is —Si(R⁸)—O-M³L¹, Q² is a single bond joined to the silicon atom ofX⁴ and Q¹ is -M⁴L⁴ _(Δ),orX⁴ is —Si(R⁸)—O-M³L¹ _(Δ), Q² is a single bond joined to the siliconatom of X⁴ and Q¹ is a single bond joined to the M³ atom of X⁴.

In a further embodiment, the metal silsesquioxane in the use accordingto the invention for selective catalysis of the gel reaction for theproduction of polyurethanes, preferably of unfoamed polyurethanes,flexible foams or rigid foams and/or in the two-component (2K) systemaccording to the invention, has the general formula

(X⁴)(Z¹Y¹X²O)(Z²X¹O₂)(Z³X³O₂)(R¹Y²SiO)(R³SiO)(R⁴SiO₂)(R²SiO₂)(Q¹)(Q²)where X¹, X² and X³ are independently selected from Si and M¹, where M¹is selected from the group consisting of s- and p-block metals, d- andf-block transition metals, lanthanide and actinide metals andsemimetals, especially from the group consisting of metals fromtransition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc,Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably fromthe group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,Z¹, Z² and Z³ are independently selected from the group consisting ofL², R⁵, R⁶ and R⁷, where L² is selected from the group consisting of —OHand —O—(C1- to C10-alkyl), especially —O—(C1-to C8-alkyl) or —O—(C1- toC6-alkyl), or where L² is selected from the group consisting of —OH,—O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and—O-isobutyl;R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are independently selected from the groupconsisting of optionally substituted C1- to C20-alkyl, optionallysubstituted C3- to C6-cycloalkyl, optionally substituted C2- toC20-alkenyl and optionally substituted C6- to C10-aryl;Y¹ and Y² are independently —O-M²-L³ _(Δ), or Y¹ and Y² are associatedand together are —O-M²(L³ _(Δ))-O— or —O—, where L³ is selected from thegroup consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- toC8-alkyl) or —O—(C1- to C6-alkyl), or where L³ is selected from thegroup consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl,—O-octyl, —O-isopropyl, and —O-isobutyl, and M² is selected from thegroup consisting of s- and p-block metals, d- and f-block transitionmetals, lanthanide and actinide metals and semimetals, especially fromthe group consisting of metals from transition group 1, 2, 3, 4, 5, 8,10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably fromthe group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga,Sn and Bi; especially preferably from the group consisting of Zn, Ti,Zr, Hf, V, Fe, Sn and Bi, andX⁴ is -M³L¹ _(Δ) or M³ and Q¹ and Q² are each H or a single bond joinedto M³, where L¹ is selected from the group consisting of —OH and —O—(C1-to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl),or where L¹ is selected from the group consisting of —OH, —O-methyl, —O—ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, andwhere M³ is selected from the group consisting of s- and p-block metals,d- and f-block transition metals, lanthanide and actinide metals andsemimetals, especially from the group consisting of metals fromtransition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc,Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably fromthe group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,orX⁴ is -M³L¹ _(Δ) and Q² is H or a single bond joined to M³ and Q¹ is H,M⁴L⁴ _(Δ) or —SiR⁸, where M4 is selected from the group consisting of s-and p-block metals, d- and f-block transition metals, lanthanide andactinide metals and semimetals, especially from the group consisting ofmetals from transition group 2, 3, 4, 5 and 8 and metals from main group1, 2, 3, 4 and 5, especially from the group consisting of Zn, Sc, Ti,Zr, Hf, V, Pt, Ga, Sn and Bi, where L⁴ is selected from the groupconsisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- toC8-alkyl) or —O—(C1- to C6-alkyl), or where L⁴ is selected from thegroup consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl,—O-octyl, —O-isopropyl, and —O-isobutyl, and where R⁸ is selected fromthe group consisting of optionally substituted C1- to C20-alkyl,optionally substituted C3- to C6-cycloalkyl, optionally substituted C2-to C20-alkenyl and optionally substituted C6- to C10-aryl,orX⁴, Q¹ and Q² are independently -M³L¹ _(Δ),orX⁴ is —Si(R⁸)—O-M³L¹ _(Δ), Q² is a single bond joined to the siliconatom of X⁴ and Q¹ is -M⁴L⁴ _(Δ),orX⁴ is —Si(R⁸)—O-M³L¹ _(Δ), Q² is a single bond joined to the siliconatom of X⁴ and Q¹ is a single bond joined to the M³ atom of X⁴.

In a further aspect of the invention, the selective catalyst used inaccordance with the invention for the gel reaction in the production ofpolyurethanes, especially of unfoamed polyurethanes, flexible foams orrigid foams and/or in the two-component (2K) system according to theinvention based on a metal-siloxane-silanol(ate) compound, may bedescribed by the structure (I)

whereX¹, X² and X³ are independently selected from Si and M¹, where M¹ isselected from the group consisting of s- and p-block metals, d- andf-block transition metals, lanthanide and actinide metals andsemimetals, especially from the group consisting of metals fromtransition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc,Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably fromthe group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,Z¹, Z² and Z³ are independently selected from the group consisting ofL², R⁵, R⁶ and R⁷, where L² is selected from the group consisting of —OHand —O—(C1- to C10-alkyl), especially —O—(C1-to C8-alkyl) or —O—(C1- toC6-alkyl), or where L² is selected from the group consisting of —OH,—O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and—O-isobutyl;R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are independently selected from the groupconsisting of optionally substituted C1- to C20-alkyl, optionallysubstituted C3- to C8-cycloalkyl, optionally substituted C2- toC20-alkenyl and optionally substituted C5- to C10-aryl;Y¹ and Y² are independently —O-M²-L³ _(Δ), or Y¹ and Y² are associatedand together are —O-M²(L³ _(Δ))-O— or —O—, where L³ is selected from thegroup consisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- toC8-alkyl) or —O—(C1- to C6-alkyl), or where L³ is selected from thegroup consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl,—O-octyl, —O-isopropyl, and —O-isobutyl, and where M² is selected fromthe group consisting of s- and p-block metals, B- and f-block transitionmetals, lanthanide and actinide metals and semimetals, especially fromthe group consisting of metals from transition group 1, 2, 3, 4, 5, 8,10 and 11 and metals from main group 1, 2, 3, 4 and 5, preferably fromthe group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga,Sn and Bi; especially preferably from the group consisting of Zn, Ti,Zr, Hf, V, Fe, Sn, Bi,and X⁴ is -M³L¹ _(Δ) or M³ and Q¹ and Q² are each H or a single bondjoined to M³, where L¹ is selected from the group consisting of —OH and—O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- toC6-alkyl), or where L¹ is selected from the group consisting of —OH, —O—methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and—O-isobutyl, and where M³ is selected from the group consisting of s-and p-block metals, d- and f-block transition metals, lanthanide andactinide metals and semimetals, especially from the group consisting ofmetals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals frommain group 1, 2, 3, 4 and 5, preferably from the group consisting of Na,Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especiallypreferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn, Bi,orX⁴ is -M³L¹ and Q² is H or a single bond joined to M³ and Q¹ is H, M⁴L⁴_(Δ) or —SiR⁸, where M⁴ is selected from the group consisting of s- andp-block metals, d- and f-block transition metals, lanthanide andactinide metals and semimetals, especially from the group consisting ofmetals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals frommain group 1, 2, 3, 4 and 5, preferably from the group consisting of Na,Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especiallypreferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn andBi, where L⁴ is selected from the group consisting of —OH and —O—(C1- toC10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), orwhere L⁴ is selected from the group consisting of —OH, —O— methyl,—O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl,and where R⁸ is selected from the group consisting of optionallysubstituted C1- to C20-alkyl, optionally substituted C3- toC6-cycloalkyl, optionally substituted C2- to C20-alkenyl and optionallysubstituted C6- to C10-aryl,orX⁴, Q¹ and Q² are independently -M³L¹ _(Δ),orX⁴ is —Si(R⁸)—O-M³L¹ _(Δ), Q² is a single bond joined to the siliconatom of X⁴ and Q¹ is -M⁴L⁴ _(Δ),orX⁴ is —Si(R⁸)—O-M³L¹ _(Δ), Q² is a single bond joined to the siliconatom of X⁴ and Q¹ is a single bond joined to the M³ atom of X4.

In a further preferred embodiment, the metal-siloxane-silanol(ate)compound in the use according to the invention for selective catalysisof the gel reaction for the production of polyurethanes, preferably ofunfoamed polyurethanes, flexible foams or rigid foams and/or in thetwo-component (2K) system according to the invention, has the generalformula (I) where X¹, X² and X³ are independently Si,

X⁴ is -M³L¹ _(Δ) and Q¹ and Q² are each a single bond joined to M³,where L¹ is selected from the group consisting of —OH and —O—(C1- toC10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1-to C6-alkyl), orwhere L¹ is selected from the group consisting of —OH, —O-methyl,—O-ethyl, —O— propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl,and where M³ is selected from the group consisting of s- and p-blockmetals, d- and f-block transition metals, lanthanide and actinide metalsand semimetals, especially from the group consisting of metals fromtransition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc,Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably fromthe group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,Z¹, Z² and Z³ are each independently selected from optionallysubstituted C1- to C20-alkyl, optionally substituted C3- toC8-cycloalkyl, optionally substituted C2- to C20-alkenyl and optionallysubstituted C5- to C10 aryl,R¹, R² and R³ are each independently selected from optionallysubstituted C1- to C20-alkyl, optionally substituted C3- toC8-cycloalkyl, optionally substituted C2- to C20-alkenyl and optionallysubstituted C5- to C10 aryl,Y¹ and Y² are associated and together form —O—.

In one embodiment, the metal-siloxane-silanol(ate) compound of formula(I) in the inventive use for selective catalysis of the gel reaction forthe production of polyurethanes, preferably of unfoamed polyurethanes,flexible foams or rigid foams and/or in the two-component (2K) systemaccording to the invention, depending on the equivalents of metalpresent, may be in mononuclear form as a monomer or in polynuclear formas a dimer (dinuclear), trimer (trinuclear), multimer (multinuclear)and/or mixtures thereof, such that, for example, structures of theformulae (Ia) to (Id) are possible.

Further polynuclear metal-siloxane-silanol(ate) compounds usable inaccordance with the invention are the structures (Ia), (Ib), (Ic) and(Id)

whereM is selected from the group consisting of s- and p-block metals, d- andf-block transition metals, lanthanide and actinide metals andsemimetals, especially from the group consisting of metals fromtransition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc,Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably fromthe group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, and each R (R¹to R⁴) is independently selected from the group consisting of optionallysubstituted C1- to C20-alkyl, optionally substituted C3- toC8-cycloalkyl, optionally substituted C2- to C20-alkenyl, optionallysubstituted C5- to C10-aryl, —OH and —O—(C1- to C10-alkyl). Thetetravalent metal M here is a shared part of multiple cages. It is knownhere to the person skilled in the art that the number of bonds to themetal M depends on the valency of the metal M. The structural formulae(Ia) to (Ic) should be adjusted correspondingly if necessary. In oneembodiment of the use according to the invention, in the production ofpolyurethanes, preferably of unfoamed polyurethanes or flexible foams, amixture of the metal-siloxane-silanol(ate) compounds of formulae (I),(Ia), (Ib) and (Ic) is used.

In addition, the polynuclear metal-siloxane-silanol(ate) compound offormula (Id) in the use according to the invention for selectivecatalysis of the gel reaction for the production of polyurethanes,preferably of unfoamed polyurethanes, flexible foams or rigid foamsand/or in the two-component (2K) system according to the invention, canhave hexacoordinated metal centres, such that structures of formula (Id)are possible,

where each M is independently selected from the group consisting of s-and p-block metals, B- and f-block transition metals, lanthanide andactinide metals and semimetals, especially from the group consisting ofmetals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals frommain group 1, 2, 3, 4 and 5, preferably from the group consisting of Na,Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especiallypreferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn andBi, and each R is independently selected from the group consisting ofoptionally substituted C1- to C20-alkyl, optionally substituted C3- toC8-cycloalkyl, optionally substituted C2- to C20-alkenyl, optionallysubstituted C5- to C10-aryl, —OH and —O—(C1- to C10-alkyl).

In the context of the invention, the term “one-cage” refers to theisolated cage structure, i.e. present in singular form, of the gelcatalyst according to the invention based on ametal-siloxane-silanol(ate) compound. Cage structures of the gelcatalyst according to the invention that are based on ametal-siloxane-silanol(ate) compound may be encompassed by the structure(IV) and likewise by the structures (I) and (II)

whereX⁴ is -M³L¹ _(Δ) where L¹ is selected from the group consisting of —OHand —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- toC6-alkyl), or where L¹ is selected from the group consisting of —OH,—O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and—O— isobutyl, and where M³ is selected from the group consisting of s-and p-block metals, d- and f-block transition metals, lanthanide andactinide metals and semimetals, especially from the group consisting ofmetals from transition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals frommain group 1, 2, 3, 4 and 5, preferably from the group consisting of Na,Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especiallypreferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn andBi,Z¹, Z² and Z³ are independently selected from the group consisting ofoptionally substituted C1- to C20-alkyl, optionally substituted C3- toC8-cycloalkyl, optionally substituted C2- to C20-alkenyl and optionallysubstituted C5- to C10-aryl;R¹, R², R³ and R⁴ are each independently selected from the groupconsisting of optionally substituted C1- to C20-alkyl, optionallysubstituted C3- to C8-cycloalkyl, optionally substituted C2- toC20-alkenyl and optionally substituted C5- to C10-aryl.

The use according to the invention further relates tometal-siloxane-silanol(ate) compounds of the general structural formula(II) that are used for selective catalysis of the gel reaction for theproduction of polyurethanes, preferably of unfoamed polyurethanes,flexible foams or rigid foams and/or in the two-component (2K) systemaccording to the invention, where X⁴ is -M³L¹ _(Δ) where L¹ is selectedfrom the group consisting of —OH and —O—(C1- to C10-alkyl), especially—O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), or where L¹ is selectedfrom the group consisting of —OH, —O-methyl, —O-ethyl, —O-propyl,—O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl, and where M³ isselected from the group consisting of s- and p-block metals, d- andf-block transition metals, lanthanide and actinide metals andsemimetals, especially from the group consisting of metals fromtransition group 1, 2, 3, 4, 5, 8, 10 and 11 and metals from main group1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc,Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably fromthe group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,

Z¹, Z² and Z³ are independently selected from the group consisting ofL², R⁵, R⁶ and R⁷, where L² is selected from the group consisting of —OHand —O—(C1- to C10-alkyl), especially —O—(C1-to C8-alkyl) or —O—(C1- toC6-alkyl), or where L² is selected from the group consisting of —OH,—O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and—O-isobutyl, andR¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are independently selected from the groupconsisting of optionally substituted C1- to C20-alkyl, optionallysubstituted C3- to C8-cycloalkyl, optionally substituted C2- toC20-alkenyl and optionally substituted C5- to C10-aryl.

In a particularly advantageous embodiment, the polyurethanes, preferablyunfoamed polyurethanes or flexible or rigid foams, may have beenproduced by selective catalysis of the gel reaction with heptaisobutylPOSS-titanium(IV) ethoxide (TiPOSS) as one metal-siloxane-silanol(ate)compound. The abbreviation “TiPOSS” here represents the monovalenttitanium-metallized silsesquioxane of the structural formula (IV) andcan be used in an equivalent manner to “heptaisobutyl POSS-titanium(IV)ethoxide” for the purposes of the invention.

In the use according to the invention, the metal-siloxane-silanol(ate)compound in the production of polyurethanes, preferably of unfoamedpolyurethanes, flexible foams or rigid foams, may be a mixturecomprising structures (I), (Ia), (Ib), (Ic), (Id), (II), (IV), (IVb),(IVc).

In a preferred embodiment, the metal in the metal-siloxane-silanol(ate)compound is a titanium.

In a further-preferred embodiment, in the production of polyurethanes,preferably of unfoamed polyurethanes, flexible foams or rigid foamsand/or in the two-component (2K) system according to the invention byuse of a metal-siloxane-silanol(ate) compound, a catalyst mayadditionally be present that is selected from the group consisting ofmetal-siloxane-silanol(ate) compounds, such as heptaisobutylPOSS-titanium(IV) ethoxide (TiPOSS), heptaisobutyl POSS-tin(IV) ethoxide(SnPOSS), tetraalkyl titanates, such as tetramethyl titanate, tetraethyltitanate, tetra-n-propyl titanate, tetraisopropyl titanate,tetra-n-butyl titanate, tetraisobutyl titanate, tetra-sec-butyltitanate, tetraoctyl titanate, tetra(2-ethylhexyl) titanate, dialkyltitanates ((RO)₂TiO₂ in which R is, for example, isopropyl, n-butyl,isobutyl), such as isopropyl n-butyl titanate; titanium acetylacetonatechelates, such as diisopropoxybis(acetylacetonate) titanate,diisopropoxybis(ethylacetylacetonate) titanate,di-n-butylbis(acetylacetonate) titanate,di-n-butyl-bis(ethylacetoacetat) titanate,triisopropoxidebis(acetylacetonate) titanate, zirconium tetraalkoxides,such as zirconium tetraethoxide, zirconium tetrabutoxide, zirconiumtetrabutyrate, zirconium tetrapropoxide, zirconium carboxylate, such aszirconium diacetate; zirconium acetylacetonate chelates, such aszirconium tetra(acetylacetonate), tributoxyzirconium acetylacetonate,dibutoxyzirconium (bisacetylacetonate), aluminium trisalkoxides, such asaluminium triisopropoxide, aluminium trisbutoxide; aluminiumacetylacetonate chelates, such as aluminium tris(acetylacetonate) andaluminium tris(ethylacetylacetonate), organotin compounds such asdibutyltin dilaurate (DBTL), dibutyltin maleate, dibutyltin diacetate,tin(II) 2-ethylhexanoate (tin octoate), tin naphthenate, dimethyltindineodecanoate, dioctyltin dineodecanoate, dimethyltin dioleate,dioctyltin dilaurate, dimethyl mercaptide, dibutyl mercaptide, dioctylmercaptide, dibutyltin dithioglycolate, dioctyltin glycolate,dimethyltin glycolate, a solution of dibutyltin oxide, reaction productsof zinc salts and organic carboxylic acids (carboxylates), such aszinc(II) 2-ethylhexanoate or zinc(II) neodecanoate, mixtures of bismuthcarboxylates and zinc carboxylates, reaction products of bismuth saltsand organic carboxylic acids, such as bismuth(III)tris(2-ethylhexanoate) and bismuth(III) tris(neodecanoate) and bismuthcomplexes, organolead compounds such as lead octoxide, organovanadiumcompounds, amine compounds such as butylamine, octylamine, dibutylamine,monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine,oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine,xylylenediamine, triethylendiamine, guanidine, diphenylguanidine,2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine,2-ethyl-4-methylimidazole and 1,8-diazabicylo(5.4.0)undecene-7 (DBU),salts of these amines with carboxylic acids or other acids or mixturesthereof, preferably metal-siloxane-silanol(ate) compounds, especiallyheptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS), dibutyltin dilaurate(DBTL), tin(II) 2-ethylhexanoate (tin octoate), zinc(II)2-ethylhexanoate, zinc(II) neodecanoate, bismuth(III)tris(2-ethylhexanoate), bismuth(III) tris(neodecanoate) or mixturesthereof, more preferably metal-siloxane-silanol(ate) compounds,especially heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS) orheptaisobutyl POSS-tin(IV) ethoxide (SnPOSS), dibutyltin dilaurate(DBTL) or mixtures thereof, most preferably heptaisobutylPOSS-titanium(IV) ethoxide (TiPOSS), heptaisobutyl POSS-tin(IV) ethoxide(SnPOSS), dibutyltin dilaurate (DBTL) or mixtures thereof.

In one embodiment of an inventive use of metal-siloxane-silanol(ate)compounds for selective catalysis of the gel reaction in the productionof polyurethanes, preferably of unfoamed polyurethanes, flexible foamsor rigid foams and/or of a two-component (2K) system according to theinvention, at least one isocyanate reactive compound (component A) isselected from the group consisting of compounds having NH, OH or SHfunctions, and one or more compounds having at least one isocyanategroup (component B) is selected from the group consisting of isocyanates(Iso) and at least one mononuclear metal-siloxane-silanol(ate) compound.

In a preferred embodiment of an inventive use ofmetal-siloxane-silanol(ate) compounds for selective catalysis of the gelreaction in the production of polyurethanes, preferably of unfoamedpolyurethanes, flexible foams or rigid foams and/or of a two-component(2K) system according to the invention, at least onehydroxy-functionalized polymer (component A) selected from the groupconsisting of polyoxyalkylene polyols, styrene-acrylonitrile, graftedpolyether polyols, polyester polyols, polycarbonate polyols,polyhydroxy-functional fats and/or oils, polyhydrocarbon polyols ormixtures thereof, and one or more compounds having at least oneisocyanate group (component B) selected from the group of polymericmethylene diphenyl isocyanate (polyMDI or PMDI), 4,4′-methylene diphenylisocyanate (4,4′-MDI), 2,4-methylene diphenyl isocyanate, (2,4-MDI),2,2′-methylene diphenyl isocyanate (2,2-MDI), NCO prepolymers based onthe aforementioned MDI isomers, isophorone diisocyanate (IPDI), tolylene2,4- and/or 2,6-diisocyanate (TDI), hexamethylene 1,6-diisocyanate (HDI)or the trimer thereof (HDI trimer) or mixtures thereof, catalysed by atleast one mononuclear one-cage metal-siloxane-silanol(ate) compound, isused.

In a further-preferred embodiment of an inventive use ofmetal-siloxane-silanol(ate) compounds for selective catalysis of the gelreaction in the production of polyurethanes, preferably of unfoamedpolyurethanes, flexible foams or rigid foams and/or a two-component (2K)system according to the invention, at least one hydroxy-functionalizedpolymer (component A) selected from the group of polyoxyalkylenepolyols, polyester polyols, polycarbonate polyols,polyhydroxy-functional fats and/or oils, or mixtures thereof, and one ormore compounds having at least one isocyanate group (component B),selected from the group of polymeric methylene diphenyl isocyanate(polyMDI or PMDI), 4,4′-methylene diphenyl isocyanate (4,4′-MDI),isophorone diisocyanate (IPDI), or mixtures thereof, catalysed by atleast one mononuclear titanium-siloxane-silanol(ate) compound,especially by heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS), isused.

In a very particularly preferred embodiment of a two-component (2K)system according to the invention, a gel reaction catalysed byheptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS) of a component Aselected from the group consisting of polyalkylene diols, polyesterpolyols, or mixtures thereof, with a component B selected from the groupconsisting of polymeric methylene diphenyl isocyanate (polyMDI),4,4′-methylene diphenyl isocyanate (4,4′-MDI), isophorone diisocyanate(IPDI) or mixtures thereof is employed.

In the most preferred embodiment, all the above uses according to theinvention and/or two-component (2K) systems include heptaisobutylPOSS-titanium(IV) ethoxide (TiPOSS) in the selective catalysis of thegel reaction in the production of polyurethanes, preferably the unfoamedpolyurethanes, flexible foams or rigid foams.

In an alternative embodiment, all the above uses according to theinvention and/or two-component (2K) systems include, rather thanheptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS), heptaisobutyl POSStin(IV) ethoxide(SnPOSS) or a mixture thereof. In what is, however, themost preferred embodiment, solely heptaisobutyl POSS-titanium(IV)ethoxide (TiPOSS) is present in the uses according to the inventionand/or in the two-component (2K) system.

The inventive two-component (2K) systems and uses of all the abovecombinations, in a preferred embodiment, include a further catalystselected from metal-siloxane-silanol(ate) compounds, especiallyheptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS) or heptaisobutylPOSS-tin(IV) ethoxide (SnPOSS), dibutyltin dilaurate (DBTL) or mixturesthereof.

In an alternative preferred embodiment, all the above systems of theinvention, especially two-component (2K) systems, combinations or uses,include dibutyltin dilaurate (DBTL) or heptaisobutyl POSS-tin(IV)ethoxide (SnPOSS) as second catalyst.

In a further-preferred embodiment, the use according to the invention,as well as the metal-siloxane-silanol(ate) compounds for selectivecatalysis of the gel reaction in the production of polyurethanes,preferably of unfoamed polyurethanes, flexible foams or rigid foamsand/or the two-component (2K) system according to the invention, alsocomprises additives such as one or more fillers selected from the groupof inorganic and organic fillers, especially natural, ground orprecipitated calcium carbonates optionally coated with fatty acids,especially stearic acid, barite (heavy spar), talcs, quartz flours,quartz sand, dolomites, wollastonites, kaolins, calcined kaolins, mica(potassium aluminium silicate), molecular sieves, aluminium oxides,aluminium hydroxides, magnesium hydroxide, silicas including finelydivided silicas from pyrolysis processes, industrially produced carbonblacks, graphite, metal powders such as aluminium, copper, iron, silveror steel, PVC powders or hollow beads, one or more adhesion promotersfrom the group of the silanes, especially aminosilanes such as3-aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane,N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane,N-(2-aminoethyl)-N′-[3-(trimethoxysilyl)propyl]ethylenediamine andanalogues thereof having methoxy or isopropoxy in place of the methoxygroups on the silicon, aminosilanes having secondary amino groups, suchas, in particular, N-phenyl-, N-cyclohexyl- and N-alkylaminosilanes, andalso mercaptosilanes, epoxysilanes, (meth)acryloylsilanes,anhydridosilanes, carbamatosilanes, alkylsilanes and iminosilanes, andoligomeric forms of these silanes, and adducts of primary aminosilaneswith epoxysilanes or (meth)acryloylsilanes or anhydridosilanes.Especially suitable are 3-glycidoxypropyltrimethoxysilane,3-aminopropyltrimethoxysilane,N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,N-(2-aminoethyl)-N′-[3-(trimethoxysilyl)propyl]ethylenediamine,3-mercaptopropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane and thecorresponding silanes having ethoxy groups in places of the methoxygroups, and oligomeric forms of these silanes, one or more moisturescavengers from the group of silanes, especially tetraethoxysilane,vinyltrimethoxy- or vinyltriethoxysilane or organoalkoxysilanes having afunctional group in the a position to the silane group, especiallyN-(methyldimethoxysilylmethyl)-O-methyl carbamate,(methacryloyloxymethyl)silanes, methoxymethylsilanes, orthoformicesters, and calcium oxide or molecular sieves, one or more plasticizersfrom the group of carboxylic esters, such as phthalates, especiallydiisononyl cyclohexane-1,2-dicarboxylate, dioctyl phthalate, diisononylphthalate or diisodecyl phthalate, adipates, especially dioctyl adipate,azelates, sebacates, polyols, especially polyoxyalkylene polyols orpolyester polyols, glycol ethers, glycol esters, citrates, especiallytriethyl citrate, organic phosphoric and sulfonic esters, polybutenes,or fatty acid methyl or ethyl esters derived from natural fats or oils,one or more UV stabilizers from the group of organic (benzophenones,benzotriazoles, oxalanilides, phenyltriazines) and inorganic (titaniumdioxide, iron oxide, zinc oxide) UV absorbers, and antioxidants from thegroup of sterically hindered phenols, amines, phosphites andphosphonites, one or more thixotropic agents from the group of sheetsilicates such as bentonites, derivatives of castor oil, hydrogenatedcastor oil, polyamides, polyurethanes, urea compounds, fumed silicas,cellulose ethers or hydrophobically modified polyoxyethylenes, one ormore wetting agents selected from the group of nonionic, anionic andcationic surfactants, or combinations of these.

In a further embodiment, the inventive two-component (2K) system,especially for unfoamed polyurethanes, additionally includes a waterscavenger, preferably a molecular sieve, UOP-L powder, vinylalkoxysilaneor mixtures thereof, more preferably vinyltrimethoxysilane (VTMO), UOP-Lpowder or mixtures thereof, most preferably UOP-L powder.

In one embodiment, the system, especially the two-component (2K) system,in a use according to the invention comprises a water scavenger. Theproportion here of the water scavenger is not more than 5.0% by weight,preferably not more than 3.5% by weight, more preferably not more than2.5% by weight, even more preferably not more than 1.5% by weight,exceptionally preferably not more than 1% by weight, based on theoverall composition of the system.

In a preferred embodiment, the system, especially the two-component (2K)system, in the overall composition of a use according to the inventioncomprises, as water scavenger, at least one molecular sieve, especiallyUOP-L powder, in a proportion of not more than 5.0% by weight,preferably not more than 3.5% by weight, more preferably not more than2.5% by weight, most preferably not more than 2.0% by weight, or atleast one monooxazolidine, especially Incozol®, in a proportion of notmore than 4% by weight, preferably not more than 2.5% by weight, morepreferably not more than 2% by weight, most preferably not more than1.5% by weight, or at least one organoalkoxysilane, especiallyvinyltrimethoxysilane, or alkoxysilanes, especially tetraethoxysilane,in a proportion of not more than 3% by weight, preferably not more than2.0% by weight, more preferably not more than 1.5% by weight, mostpreferably not more than 1.25% by weight, or p-tosyl isocyanate in aproportion of not more than 4% by weight, preferably not more than 3% byweight, more preferably not more than 2.5% by weight, most preferablynot more than 2% by weight, or calcium oxide in a proportion of not morethan 3% by weight, preferably not more than 2% by weight, morepreferably not more than 1.5% by weight, most preferably not more than1.25% by weight, or at least one orthoformic ester, especially triethylorthoformate (TEOF), in a proportion of not more than 3% by weight,preferably not more than 2% by weight, more preferably not more than1.5% by weight, most preferably not more than 1.25% by weight, ormixtures thereof.

In a particularly preferred embodiment, the system, especially thetwo-component (2K) system, especially for unfoamed polyurethanes in ause according to the invention, does not include any water scavenger.

In a further, very particularly preferred embodiment, the density of theunfoamed polyurethanes is ≥1000 kg/m³ when the total water content is≤0.6%, preferably 0.6%, in the production thereof.

A preferred embodiment of a process according to the invention forproduction of unfoamed polyurethanes comprises the following steps:

-   -   (i) providing a component A comprising at least one        hydroxy-functionalized polymer according to any of the above        definitions,    -   (ii) providing a component B comprising at least one compound        having one or more isocyanate groups according to any of the        above definitions,    -   (iii) adding at least one metal-siloxane-silanol(ate) compound        according to any of the above definitions to component A or B,    -   (iv) optionally adding a water scavenger, preferably a molecular        sieve or UOP-L powder or mixtures thereof, more preferably UOP-L        powder, to at least one of components A and/or B,    -   (v) optionally adding at least one additive according to any of        the above definitions to at least one of components A and/or B,    -   (vi) combining component A with component B.

A particularly preferred embodiment of a process according to theinvention for production of unfoamed polyurethanes comprises thefollowing steps:

-   -   (i) providing a component A comprising at least one        hydroxy-functionalized polymer selected from the group        consisting of difunctional or higher-functionality        polyoxyalkylene polyols, polyester polyols, polycarbonate        polyols, polyhydroxy-functional fats and/or oils, or mixtures        thereof, preferably with number-average molar masses (Mn) of        250-35 000 g/mol, more preferably of about 350 g/mol or about 19        000 g/mol, or mixtures thereof, and at least one        metal-siloxane-silanol(ate) compound, especially heptaisobutyl        POSS-titanium(IV) ethoxide (TiPOSS), heptaisobutyl POSS-tin(IV)        ethoxide (SnPOSS) or mixtures thereof,    -   (ii) providing a component B comprising one or more isocyanates        (Iso) selected from the group consisting of polymeric methylene        diphenyl isocyanate (polyMDI), 4,4′-methylene diphenyl        isocyanate (4,4′-MDI), isophorone diisocyanate (IPDI) or        mixtures thereof,    -   (iii) optionally adding a water scavenger, preferably a        molecular sieve or UOP-L powder or mixtures thereof, more        preferably UOP-L powder, to at least one of components A and/or        B,    -   (iv) optionally adding at least one additive according to any of        the above definitions to at least one components A and/or B,    -   (v) combining component A with component B.

An alternative preferred embodiment of a process according to theinvention for production of flexible or rigid foams comprises thefollowing steps:

-   -   (i) providing a component A comprising at least one        hydroxy-functionalized polymer according to any of the preceding        embodiments,    -   (ii) providing a component B comprising at least one compound        having one or more isocyanate groups according to any of the        preceding embodiments,    -   (iii) adding at least one metal-siloxane-silanol(ate) compound        according to any of the preceding claims to component A and/or        B,    -   (iv) optionally adding a water scavenger according to any of the        preceding embodiments to at least one of components A and/or B,    -   (v) optionally adding at least one additive according to any of        the preceding embodiments to at least one of components A and/or        B,    -   (vi) adding a blowing agent to at least one of components A        and/or B according to any of the preceding embodiments,    -   (vii) combining component A with component B.

A particularly preferred embodiment of a process according to theinvention for production of flexible or rigid foams comprises thefollowing steps:

-   -   (i) providing a component A comprising at least one        hydroxy-functionalized polymer selected from the group        consisting of EO-tipped polyether triols, difunctional or        higher-functional polyoxyalkylene polyols, polyester polyols,        polycarbonate polyols, polyhydroxy-functional fats and/or oils,        preferably EO-tipped polyether triols, difunctional or        higher-functional polyoxyalkylene polyols, polyester polyols, or        mixtures thereof,    -   (ii) providing a component B comprising at least one compound        having one or more isocyanate groups, selected from the group        consisting of polymeric methylene diphenyl isocyanate (polyMDI),        4,4′-methylene diphenyl isocyanate (4,4′-MDI), isophorone        diisocyanate (IPDI) or mixtures thereof,    -   (iii) adding at least one metal-siloxane-silanol(ate) compound,        especially heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS),        heptaisobutyl POSS-tin(IV) ethoxide (SnPOSS) or mixtures        thereof, to component A and/or B,    -   (iv) optionally adding a water scavenger, preferably a molecular        sieve or UOP-L powder or mixtures thereof, more preferably UOP-L        powder, to at least one of components A and/or B,    -   (v) optionally adding at least one additive according to any of        the above definitions to at least one of components A and/or B,    -   (vi) adding a blowing agent to at least one of components A        and/or B, selected from the group consisting of water, nitrogen,        air, carbon dioxide, pentane, hydrofluorocarbons (HFCs) or        mixtures thereof, preferably water or mixtures thereof,    -   (vii) combining component A with component B.

A preferred embodiment of a combination for production of unfoamedpolyurethanes comprising at least one component A and component B, wherecomponent A comprises at least one hydroxy-functionalized polymeraccording to any of the preceding claims and at least onemetal-siloxane-silanol(ate) compound according to any of the precedingclaims, and component B comprises at least one compound having one ormore isocyanate groups according to any of the preceding claims,characterized in that components A and B are each present separately andin a relative ratio of 2:1 up to 1:2, preferably in a ratio of 1.8:1 to1:1.8, more preferably in a ratio of 1.5:1 up to 1:1.5, most preferablyin a ratio of 1.2:1 up to 1:1.2.

An alternative preferred embodiment of a combination for production ofrigid or flexible foams comprising at least one component A andcomponent B, where component A comprises at least onehydroxy-functionalized polymer according to any of the preceding claimsand at least one metal-siloxane-silanol(ate) compound according to anyof the preceding claims, and component B comprises at least one compoundhaving one or more isocyanate groups according to any of the precedingclaims, characterized in that components A and B are each presentseparately and in a relative ratio of 2:1 up to 1:2, preferably in aratio of 1.8:1 to 1:1.8, more preferably in a ratio of 1.5:1 up to1:1.5, most preferably in a ratio of 1.2:1 up to 1:1.2.

The process according to the invention is preferably conducted attemperatures of at least 0° C., more preferably at least 20° C., andpreferably at most 150° C., especially at most 80° C.

The process according to the invention can be effected continuously, bymeans of conventional high-pressure and low-pressure mixing systemshaving multiple metering sites in parallel or else in series, orbatchwise, for example in a conventional reaction tank with stirrersystem.

In one embodiment, unfoamed polyurethanes are producible by a processusing at least one metal-siloxane-silanol(ate) compound, preferably amononuclear one-cage structure according to any of structures (IV),(IVb) or (IVc), more preferably a titanium-containing one-cage structureaccording to one of structures (IV), (IVb) or (IVc), most preferablyTiPOSS.

In one embodiment of the unfoamed polyurethanes according to theinvention, these are elastomers.

In a further embodiment of the unfoamed polyurethanes according to theinvention, these are thermosets.

In an alternative embodiment, foamed polyurethanes, especially flexibleor rigid foams, are producible by a process using at least onemetal-siloxane-silanol(ate) compound, preferably a mononuclear one-cagestructure according to any of structures (IV), (IVb) or (IVc), morepreferably a titanium-containing one-cage structure according to one ofstructures (IV), (IVb) or (IVc), most preferably TiPOSS.

In an advantageous embodiment of the use of at least onemetal-siloxane-silanol(ate) compound, preferably a mononuclear one-cagestructure according to any of structures (IV), (IVb) or (IVc), morepreferably a titanium-containing one-cage structure according to any ofstructures (IV), (IVb) or (IVc), most preferably TiPOSS, in theproduction of polyurethanes, these polyurethanes are particularlysuitable for use in CASE applications (coatings, adhesives, sealants andelastomers) and/or elastomer materials.

In a further advantageous embodiment of the use of at least onemetal-siloxane-silanol(ate) compound, preferably a mononuclear one-cagestructure according to any of structures (IV), (IVb) or (IVc), morepreferably a titanium-containing one-cage structure according to any ofstructures (IV), (IVb) or (IVc), most preferably TiPOSS, in theproduction of flexible foams, these flexible foams are particularlysuitable for use in furniture, mattresses, car seats, gasket materialsor acoustic materials.

In a further advantageous embodiment of the use of at least onemetal-siloxane-silanol(ate) compound, preferably a mononuclear one-cagestructure according to any of structures (IV), (IVb) or (IVc), morepreferably a titanium-containing one-cage structure according to any ofstructures (IV), (IVb) or (IVc), most preferably TiPOSS, in theproduction of rigid foams, these rigid foams are particularly suitablefor use in sound insulations, heat insulations and/or cold insulations.

In a further advantageous embodiment of the use of at least onemetal-siloxane-silanol(ate) compound, preferably a mononuclear one-cagestructure according to any of structures (IV), (IVb) or (IVc), morepreferably a titanium-containing one-cage structure according to any ofstructures (IV), (IVb) or (IVc), most preferably TiPOSS, in theproduction of rigid foams, these rigid foams are particularly suitablefor use in district heating pipes, tanks and pipelines, and forproduction of all kinds of refrigeration units.

In a further advantageous embodiment of the use of at least onemetal-siloxane-silanol(ate) compound, preferably a mononuclear one-cagestructure according to any of structures (IV), (IVb) or (IVc), morepreferably a titanium-containing one-cage structure according to any ofstructures (IV), (IVb) or (IVc), most preferably TiPOSS, in theproduction of rigid foams, these rigid foams are particularly suitablefor use in insulation panels for the fields of use of roofs, walls,floors and/or ceilings, in window frame insulations or as assembly foam.

PARTICULARLY PREFERRED EMBODIMENTS OF THE INVENTION

-   1. Use of at least one metal-siloxane-silanol(ate) catalyst for    selective catalysis of the gel reaction in a system for the    production of polyurethanes.-   2. Use of at least one metal-siloxane-silanol(ate) compound for the    production of unfoamed polyurethanes, especially of elastomers    and/or encapsulating compounds.-   3. Use of at least one metal-siloxane-silanol(ate) compound for    production of flexible foams, especially flexible polyurethane    foams.-   4. Use of at least one metal-siloxane-silanol(ate) compound for    production of rigid foams, especially rigid polyurethane foams.-   5. Use according to any of the preceding claims, wherein the system    is a two-component (2K) system.-   6. Use according to Embodiment 5, characterized in that the    two-component (2K) system comprises a component A and a component B,    where the metal-siloxane-silanol(ate) compound(s) is/are formulated    preferably together with component A comprising at least one    hydroxy-functionalized polymer or with component B comprising at    least one compound having one or more isocyanate groups.-   7. Use according to Embodiment 2, 5 or 6, wherein the unfoamed    polyurethane has a density in the range according to DIN EN ISO    845:2009-10 of 800 to 1950 kg/m³, preferably in the range from 950    to 1750 kg/m³, more preferably in the range from 980 to 1650 kg/m³,    most preferably in the range from 990 to 1600 kg/m³.-   8. Use according to Embodiment 2 or 5 to 7, wherein the unfoamed    polyurethane has a Shore 00 hardness according to ASTM D2240-15 in    the range of 40-100, preferably in the range from 45 to 95,    preferably in the range from 50 to 90, especially preferably in the    range from 55 to 85.-   9. Use according to Embodiment 2, 5 or 6 to 8, wherein the unfoamed    polyurethane has a Shore A hardness according to ASTM D2240-15 in    the range of 0-100, preferably in the range from 5 to 95, preferably    in the range from 10 to 90, especially preferably in the range from    15 to 85.-   10. Use according to Embodiment 2, 5 or 6 to 9, wherein the unfoamed    polyurethane has a Shore D hardness according to ASTM D2240-15 in    the range of 0-100, preferably in the range from 5 to 95, preferably    in the range from 10 to 90, especially preferably in the range from    15 to 85.-   11. Use according to Embodiment 3, wherein the flexible foam has a    density according to DIN EN ISO 845:2009-10 in the range from 50 to    900 kg/m³, preferably in the range from 100 to 850 kg/m³, more    preferably in the range from 200 to 750 kg/m³, most preferably in    the range from 200 to 700 kg/m³.-   12. Use according to Embodiment 3, 5, 6 or 11, wherein the flexible    foam has a Shore 00 hardness according to ASTM D2240-15 in the range    of 0-100, preferably in the range from 5 to 95, preferably in the    range from 15 to 90, especially preferably in the range from 20 to    85.-   13. Use according to Embodiment 3, 5, 6 or 11 to 12, wherein the    flexible foam has a Shore A hardness according to ASTM D2240-15 in    the range of 0-100, preferably in the range from 20 to 95,    preferably in the range from 20 to 60, especially preferably in the    range from 20 to 50.-   14. Use according to Embodiment 3, 5, 6 or 11 to 13, wherein the    flexible foam has a tensile strength according to DIN EN ISO    1798:2008-04 of between 180 and 400 kPa, preferably between 200 and    380 kPa, more preferably between 200 and 350 kPa.-   15. Use according to Embodiment 4, wherein the rigid foam has a    density according to DIN EN ISO 845:2009-10 in the range from 50 to    900 kg/m³, preferably in the range from 150 to 850 kg/m³, more    preferably in the range from 200 to 750 kg/m³, most preferably in    the range from 200 to 700 kg/m³-   16. Use according to Embodiment 5 to 6 to 15, wherein the rigid foam    has a Shore D hardness according to ASTM D2240-15 in the range from    0 to 100, preferably in the range from 15 to 100, preferably in the    range from 20 to 95, especially preferably in the range from 25 to    90.-   17. Use according to Embodiment 5 to 6 or 15 to 16, wherein the    flexible foam has a tensile strength according to ISO 1926:2009-12    of between 100 and 2500 kPa, preferably between 150 and 2250 kPa,    more preferably between 200 and 2000 kPa.-   18. Use according to any of the preceding embodiments, characterized    in that the system comprises a water scavenger and the proportion of    the water scavenger is not more than 5.0% by weight, preferably not    more than 3.5% by weight, more preferably not more than 2.5% by    weight, very preferably not more than 1.5% by weight, extremely    preferably not more than 1% by weight, of the total composition of    the system.-   19. Use according to Embodiment 18, characterized in that the system    does not include any water scavenger.-   20. Use according to any of the preceding embodiments, characterized    in that the metal-siloxane-silanol(ate) compound is in the form of a    monomer, oligomer and/or polymer, where the metal(s) are present    terminally and/or within the chain.-   21. Use according to any of the preceding embodiments, characterized    in that the metal-siloxane-silanol(ate) compound has the general    formula R*_(q)Si_(r)O_(s)M_(t) where each R* is independently    selected from the group consisting of optionally substituted C1- to    C20-alkyl, optionally substituted C3- to C6-cycloalkyl, optionally    substituted C2- to C20-alkenyl, optionally substituted C6- to    C10-aryl, —OH and —O—(C1- to C10-alkyl), each M is independently    selected from the group consisting of s- and p-block metals, d- and    f-block transition metals, lanthanide and actinide metals and    semimetals, especially from the group consisting of metals of    transition groups 1, 2, 3, 4, 5, 8, 10 and 11 and metals of main    groups 1, 2, 3, 4 and 5, preferably from the group consisting of Na,    Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially    preferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn    and Bi,    -   q is an integer from 4 to 19,    -   r is an integer from 4 to 10,    -   s is an integer from 8 to 30, and    -   t is an integer from 1 to 8.-   22. Use according to any of the preceding embodiments, characterized    in that the metal-siloxane-silanol(ate) compound has a general    structure (I)

whereX¹, X² and X³ are independently selected from Si and M¹, where M¹ isselected from the group consisting of s- and p-block metals, d- andf-block transition metals, lanthanide and actinide metals andsemimetals, especially from the group consisting of metals of transitiongroups 1, 2, 3, 4, 5, 8, 10 and 11 and metals of main groups 1, 2, 3, 4and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr,Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the groupconsisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,Z¹, Z² and Z³ are independently selected from the group consisting ofL², R⁵, R⁶ and R⁷, where L² is selected from the group consisting of —OHand —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- toC6-alkyl), or where L² is selected from the group consisting of —OH,—O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and—O— isobutyl;R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are independently selected from the groupconsisting of optionally substituted C1- to C20-alkyl, optionallysubstituted C3- to C8-cycloalkyl, optionally substituted C2- toC20-alkenyl and optionally substituted C5- to C10-aryl; Y¹ and Y² areindependently —O-M²-L³ _(Δ), or Y¹ and Y² are associated and togetherare —O-M²(L³ _(Δ))-O— or —O—, where L³ is selected from the groupconsisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- toC8-alkyl) or —O—(C1- to C6-alkyl), or where L³ is selected from thegroup consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl,—O-octyl, —O— isopropyl, and —O-isobutyl, and where M² is selected fromthe group consisting of s- and p-block metals, d- and f-block transitionmetals, lanthanide and actinide metals and semimetals,especially from the group consisting of metals of transition groups 1,2, 3, 4, 5, 8, 10 and 11 and metals of main groups 1, 2, 3, 4 and 5,preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V,Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the groupconsisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,andX⁴ is -M³L¹ _(Δ) or M³ and Q¹ and Q² are H or each is a single bondjoined to M³, where L¹ is selected from the group consisting of —OH and—O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- toC6-alkyl), or where L¹ is selected from the group consisting of —OH,—O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and—O-isobutyl, and where M³ is selected from the group consisting of s-and p-block metals, d- and f-block transition metals, lanthanide andactinide metals and semimetals,especially from the group consisting of metals of transition groups 1,2, 3, 4, 5, 8, 10 and 11 and metals of main groups 1, 2, 3, 4 and 5,preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V,Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the groupconsisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi,orX⁴ is -M³L¹ _(Δ) and Q² is H or a single bond joined to M³ and Q¹ is H,M⁴L⁴ _(Δ) or —SiR⁸, where M⁴ is selected from the group consisting of s-and p-block metals, d- and f-block transition metals, lanthanide andactinide metals and semimetals, especially from the group consisting ofmetals of transition groups 1, 2, 3, 4, 5, 8, 10 and 11 and metals ofmain groups 1, 2, 3, 4 and 5, preferably from the group consisting ofNa, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especiallypreferably from the group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn andBi,and where L⁴ is selected from the group consisting of —OH and —O—(C1- toC10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), orwhere L⁴ is selected from the group consisting of —OH, —O-methyl,—O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl,and where R⁸ is selected from the group consisting of optionallysubstituted C1- to C20-alkyl, optionally substituted C3- toC8-cycloalkyl, optionally substituted C2- to C20-alkenyl and optionallysubstituted C5- to C10-aryl,orX⁴, Q¹ and Q² are independently -M³L¹ _(Δ),orX⁴ is —Si(R⁸)—O-M³L¹ _(Δ), Q² is a single bond joined to the siliconatom of X⁴ and Q¹ is -M⁴L⁴ _(Δ),orX⁴ is —Si(R⁸)—O-M³L¹ _(Δ), Q² is a single bond joined to the siliconatom of X⁴ and Q¹ is a single bond joined to the M³ atom of X⁴.

-   23. Use according to any of the preceding embodiments, characterized    in that the metal-siloxane-silanol(ate) compound has the structural    formula (II)

-   -   where X⁴, R¹, R², R³, R⁴, Z¹, Z² and Z³ are defined according to        Embodiment 22.

-   24. Use according to Embodiment 23, characterized in that the    metal-siloxane-silanol(ate) compound of the structure (IV) is a    metal silsesquioxane

-   -   where        -   X⁴ is selected from the group consisting of metals of            transition groups 1, 2, 3, 4, 5, 8, 10 and 11 and metals of            main groups 1, 2, 3, 4 and 5, preferably from the group            consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga,            Sn and Bi; especially preferably from the group consisting            of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, most preferably from            the group consisting of Ti and Sn, and is most preferably            Ti, and        -   X⁴ is joined to OR where R is selected from the group            consisting of —H, -methyl, -ethyl, -propyl, -butyl, -octyl,            -isopropyl, and -isobutyl, Z¹, Z² and Z³ are each            independently C1- to C20-alkyl, C3- to C8-cycloalkyl, C2- to            C20-alkenyl and C5- to C10-aryl, especially selected from            the group consisting of methyl, ethyl, propyl, isopropyl,            butyl, isobutyl, hexyl, heptyl, octyl, vinyl, allyl, butenyl            and phenyl, and benzyl, and R¹, R², R³ and R⁴ are each            independently C1- to C20-alkyl, C3- to C8-cycloalkyl, C2- to            C20-alkenyl, and C5- to C10-aryl, especially selected from            the group consisting of methyl, ethyl, propyl, isopropyl,            butyl, isobutyl, hexyl, heptyl, octyl, vinyl, allyl, butenyl            and phenyl, and benzyl.

-   25. Use according to Embodiment 25, characterized in that the    metal-siloxane-silanol(ate) compound is a metal silsesquioxane of    the structure (IVb)

-   -   where        -   X⁴ is selected from the group consisting of metals of            transition groups 1, 2, 3, 4, 5, 8, 10 and 11 and metals of            main groups 1, 2, 3, 4 and 5, preferably from the group            consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga,            Sn and Bi; especially preferably from the group consisting            of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, most preferably from            the group consisting of Ti (and therefore is heptaisobutyl            POSS-titanium(IV) ethoxide (TiPOSS)) and Sn (and therefore            is heptaisobutyl POSS-tin(IV) ethoxide (SnPOSS)), and is            most preferably Ti (and therefore is heptaisobutyl            POSS-titanium(IV) ethoxide (TiPOSS)).

-   26. Use according to any of the preceding embodiments, characterized    in that the hydroxy-functionalized polymer in component A is    selected from the group consisting of polyoxyalkylene diols or    polyoxyalkylene triols, especially polyoxyethylene di- and triols    and polyoxypropylene di- and triols, higher-functionality polyols    such as sorbitol, pentaerythritol-started polyols, ethylene    oxide-terminated polyoxypropylene polyols, polyester polyols,    styrene-acrylonitrile, acryloyl-methacrylate, (poly)urea-grafted or    -containing polyether polyols, polycarbonate polyols, CO₂ polyols,    polyhydroxy-functional fats and oils, especially castor oil,    polyhydrocarbon polyols such as dihydroxypolybutadiene,    polytetrahydrofuran-based polyethers (PTMEG), OH-terminated    prepolymers based on the reaction of a polyetherol or polyesterol    with a diisocyanate, polyalkylene diols, polyester polyols or    mixtures thereof, preferably polyalkylene diols, polyester polyols,    or mixtures thereof.

-   27. Use according to Embodiment 26, characterized in that the    hydroxy-functionalized polymer in component A is selected from the    group consisting of polyoxyalkylene diols, polyoxyalkylene triols,    higher-functionality polyoxyalkylene polyols, especially    polyoxyethylene di- and/or triols and/or polyoxypropylene di- and/or    triols, KOH-catalysed hydroxy-functionalized polyethers or double    metal cyanide complex-catalysed (DMC-catalysed)    hydroxy-functionalized polyethers or mixtures thereof.

-   28. Use according to any of the preceding embodiments, characterized    in that the compound having one or more isocyanate groups in    component B is selected from the group consisting of aromatic and/or    aliphatic isocyanates (Iso) of the general structure (VI) or    mixtures thereof

R^(x)—(N═C═O)_(z)  (VI)

-   -   where        -   R^(x) is a hydrocarbon-containing group, preferably at least            one aromatic or aliphatic group or mixtures thereof, more            preferably an optionally substituted straight-chain or            branched C1- to C16-alkyl group, an optionally substituted            straight-chain or branched C2- to C16-alkenyl group or an            optionally substituted straight-chain or branched C2- to            C16-alkynyl group, an optionally substituted C4- to            C14-cycloalkyl group or an optionally substituted C4- to            C14-aryl group, most preferably diphenylmethane, toluene,            dicyclohexylmethane, hexane or            methyl-3,5,5-trimethylcyclohexyl,        -   z is at least 1, preferably at least 2 or 3.

-   29. Use according to any of the preceding embodiments, characterized    in that the compound having one or more isocyanate groups in    component B is selected from the group consisting of aromatic and/or    aliphatic isocyanates (Iso) of the general structure (VI) or    mixtures thereof

R^(x)

N═C═O)_(z)  (VI)

-   -   where        -   R^(x) is diphenylmethane, toluene, dicyclohexylmethane,            hexane or methyl-3,5,5-trimethylcyclohexyl, preferably            diphenylmethane or hexane or            methyl-3,5,5-trimethylcyclohexyl, most preferably            diphenylmethane or methyl-3,5,5-trimethylcyclohexyl, and        -   z is at least 2, preferably 2 or 3

-   30. Use according to Embodiment 29, characterized in that at least    one isocyanate (Iso) of the general structure (VI) is selected from    the group consisting of polymeric, oligomeric and monomeric    methylene diphenyl isocyanate (MDI), especially of polymeric    methylene diphenyl isocyanate (poly-MDI), 4,4′-methylene diphenyl    isocyanate (4,4′-MDI), 2,4′-methylene diphenyl isocyanate    (2,4′-MDI), 2,2′-methylene diphenyl isocyanate (2,2′-MDI),    4,4′-diisocyanatodicyclohexylmethane (H₁₂MDI),    2-methylpentamethylene 1,5-diisocyanate, dodecamethylene    1,12-diisocyanate, lysine and lysine ester diisocyanate, cyclohexane    1,3-diisocyanate, cyclohexane 1,4-diisocyanate,    perhydro(diphenylmethane 2,4′-diisocyanate),    perhydro(diphenylmethane 4,4′-diisocyanate),    1,4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI),    3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (=isophorone    diisocyanate or IPDI), hexamethylene 1,6-diisocyanate (HDI) or the    trimer thereof (HDI trimer), 2,2,4- and/or    2,4,4-trimethylhexamethylene 1,6-diisocyanate,    1,4-bis(isocyanato)cyclohexane, 1,4-bis(isocyanato)benzene (PPDI),    1,3- and/or 1,4-bis(isocyanatomethyl)cyclohexane, m- and/or    p-xylylene diisocyanate (m- and/or p-XDI), m- and/or    p-tetramethylxylylene 1,3-diisocyanate, m- and/or    p-tetramethylxylylene 1,4-diisocyanate,    bis(1-isocyanato-1-methylethyl)naphthalene,    1,3-bis(isocyanato-4-methylphenyl)-2,4-dioxo-1,3-diazetidine,    naphthalene 1,5-diisocyanate (NDI),    3,3′-dimethyl-4,4′-diisocyanatodiphenyl (TODD, tolylene 2,4- and/or    2,6-diisocyanate (TDI), 1,3-bis(isocyanatomethyl)benzene or mixtures    thereof, preferably polymeric methylene diphenyl isocyanate    (poly-MDI), 4,4′-methylene diphenyl isocyanate (4,4′-MDI) or    isophorone diisocyanate (IPDI), hexamethylene 1,6-diisocyanate (HDI)    or the trimer thereof (HDI trimer) or mixtures thereof, most    preferably polymeric methylene diphenyl isocyanate (poly-MDI),    4,4′-methylene diphenyl isocyanate (4,4′-MDI) or isophorone    diisocyanate (IPDI) or mixtures thereof.

-   31. Use according to any of the preceding embodiments, characterized    in that the metal-siloxane-silanol(ate) compound has a gel/blow    reaction selectivity of >1, preferably >5, more preferably >10,    further preferably >30, most preferably >40.

-   32. Use according to any of the preceding embodiments, characterized    in that the metal-siloxane-silanol(ate) compound has a gel/blow    reaction selectivity of ≥30.

-   33. Use according to any of the preceding embodiments, characterized    in that the metal-siloxane-silanol(ate) compound is present in a    molar concentration in the range from 0.00001 to 0.06 mol/kg,    preferably in the range from 0.0002 to 0.01 mol/kg, more preferably    in the range from 0.0003% to 0.01 mol/kg, based in each case on the    total weight of the system.

-   34. Use according to any of the preceding embodiments, characterized    in that the metal-siloxane-silanol(ate) compound is present with a    proportion by weight of 0.001% to 5%, preferably in the range from    0.002% to 1%, more preferably in the range from 0.003% to 0.5%,    based in each case on the total weight of the system.

-   35. Use according to any of the preceding embodiments, characterized    in that the system cures after combination of components A and B to    give a reaction product, especially to give a polyurethane.

-   36. Use according to any of the preceding embodiments, characterized    in that the resulting reaction product has a higher density by >3%    compared to a dibutyltin dilaurate (DBTL)- or triethylenediamine    (DABCO)-catalysed resulting reaction product when the water content    of component A or component B is >0.2%.

-   37. Use according to any of the preceding embodiments, characterized    in that the system additionally comprises a catalyst selected from    the group consisting of metal-siloxane-silanol(ate) compounds, such    as heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS), heptaisobutyl    POSS-tin(IV) ethoxide (SnPOSS), tetraalkyl titanates, such as    tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate,    tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl    titanate, tetra-sec-butyl titanate, tetraoctyl titanate,    tetra(2-ethylhexyl) titanate, dialkyl titanates ((RO)₂TiO₂ in which    R is, for example, isopropyl, n-butyl, isobutyl), such as isopropyl    n-butyl titanate; titanium acetylacetonate chelates, such as    diisopropoxybis(acetylacetonate) titanate,    diisopropoxybis(ethylacetylacetonate) titanate,    di-n-butylbis(acetylacetonate) titanate,    di-n-butyl-bis(ethylacetoacetat) titanate,    triisopropoxidebis(acetylacetonate) titanate, zirconium    tetraalkoxides, such as zirconium tetraethoxide, zirconium    tetrabutoxide, zirconium tetrabutyrate, zirconium tetrapropoxide,    zirconium carboxylate, such as zirconium diacetate; zirconium    acetylacetonate chelates, such as zirconium tetra(acetylacetonate),    tributoxyzirconium acetylacetonate, dibutoxyzirconium    (bisacetylacetonate), aluminium trisalkoxides, such as aluminium    triisopropoxide, aluminium trisbutoxide; aluminium acetylacetonate    chelates, such as aluminium tris(acetylacetonate) and aluminium    tris(ethylacetylacetonate), organotin compounds such as dibutyltin    dilaurate (DBTL), dibutyltin maleate, dibutyltin diacetate, tin(II)    2-ethylhexanoate (tin octoate), tin naphthenate, dimethyltin    dineodecanoate, dioctyltin dineodecanoate, dimethyltin dioleate,    dioctyltin dilaurate, dimethyl mercaptide, dibutyl mercaptide,    dioctyl mercaptide, dibutyltin dithioglycolate, dioctyltin    glycolate, dimethyltin glycolate, a solution of dibutyltin oxide,    reaction products of zinc salts and organic carboxylic acids    (carboxylates), such as zinc(II) 2-ethylhexanoate or zinc(II)    neodecanoate, mixtures of bismuth carboxylates and zinc    carboxylates, reaction products of bismuth salts and organic    carboxylic acids, such as bismuth(III) tris(2-ethylhexanoate) and    bismuth(III) tris(neodecanoate) and bismuth complexes, organolead    compounds such as lead octoxide, organovanadium compounds, amine    compounds such as butylamine, octylamine, dibutylamine,    monoethanolamine, diethanolamine, triethanolamine,    diethylenetriamine, oleylamine, cyclohexylamine, benzylamine,    diethylaminopropylamine, xylylenediamine, triethylendiamine,    guanidine, diphenylguanidine, 2,4,6-tris(dimethylaminomethyl)phenol,    morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole and    1,8-diazabicylo(5.4.0)undecene-7 (DBU), salts of these amines with    carboxylic acids or other acids or mixtures thereof, preferably    metal-siloxane-silanol(ate) compounds, especially heptaisobutyl    POSS-titanium(IV) ethoxide (TiPOSS), dibutyltin dilaurate (DBTL),    tin(II) 2-ethylhexanoate (tin octoate), zinc(II) 2-ethylhexanoate,    zinc(II) neodecanoate, bismuth(III) tris(2-ethylhexanoate),    bismuth(III) tris(neodecanoate) or mixtures thereof, more preferably    metal-siloxane-silanol(ate) compounds, especially heptaisobutyl    POSS-titanium(IV) ethoxide (TiPOSS) or heptaisobutyl POSS-tin(IV)    ethoxide (SnPOSS), dibutyltin dilaurate (DBTL) or mixtures thereof,    most preferably heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS),    heptaisobutyl POSS-tin(IV) ethoxide (SnPOSS), dibutyltin dilaurate    (DBTL) or mixtures thereof.

-   38. Use according to any of the preceding embodiments, wherein the    blowing agent is selected from the group consisting of water, air,    nitrogen, carbon dioxide, pentane, cyclopentane, hydrofluorocarbons    and mixtures thereof.

-   39. Use according to any of the preceding embodiments, wherein the    system further comprises one or more additives selected from the    group comprising filler, an adhesion promoter, plasticizers, UV    stabilizers, thixotropic agents, wetting agents or combinations    thereof.

-   40. Two-component (2K) system defined according to any of the    preceding embodiments.

-   41. Process for producing unfoamed polyurethane, comprising the    following steps:    -   (i) providing a component A comprising at least one        hydroxy-functionalized polymer according to any of the preceding        embodiments,    -   (ii) providing a component B comprising at least one compound        having one or more isocyanate groups according to any of the        preceding embodiments,    -   (iii) adding at least one metal-siloxane-silanol(ate) compound        according to any of the preceding embodiments to component A or        B,    -   (iv) optionally adding a water scavenger according to any of the        preceding embodiments to at least one of components A and/or B,    -   (v) optionally adding at least one additive according to any of        the preceding embodiments to at least one of components A and/or        B,    -   (vi) combining component A with component B.

-   42. Process for producing flexible foams, comprising the following    steps:    -   (i) providing a component A comprising at least one        hydroxy-functionalized polymer according to any of the preceding        embodiments,    -   (ii) providing a component B comprising at least one compound        having one or more isocyanate groups according to any of the        preceding embodiments,    -   (iii) adding at least one metal-siloxane-silanol(ate) compound        according to any of the preceding embodiments to component A        and/or B,    -   (iv) optionally adding a water scavenger according to any of the        preceding embodiments to at least one of components A and/or B,    -   (v) optionally adding at least one additive according to any of        the preceding embodiments to at least one of components A and/or        B,    -   (vi) adding a blowing agent to at least one of components A and        B according to any of the preceding embodiments,    -   (vii) combining component A with component B.

-   43. Process for producing rigid foams, comprising the following    steps:    -   (i) providing a component A comprising at least one        hydroxy-functionalized polymer according to any of the preceding        embodiments,    -   (ii) providing a component B comprising at least one compound        having one or more isocyanate groups according to any of the        preceding embodiments,    -   (iii) adding at least one metal-siloxane-silanol(ate) compound        according to any of the preceding embodiments to component A        and/or B,    -   (iv) optionally adding a water scavenger according to any of the        preceding embodiments to at least one of components A and/or B,    -   (v) optionally adding at least one additive according to any of        the preceding embodiments to at least one of components A and/or        B,    -   (vi) adding a blowing agent to at least one of components A and        B according to any of the preceding embodiments,    -   (vii) combining component A with component B.

-   44. Combination for production of unfoamed polyurethanes, comprising    at least one component A and component B, where component A    comprises at least one hydroxy-functionalized polymer according to    any of the preceding embodiments and at least one    metal-siloxane-silanol(ate) compound according to any of the    preceding embodiments, and component B comprises at least one    compound having one or more isocyanate groups according to any of    the preceding embodiments, characterized in that components A and B    are each present separately and in a relative NCO:OH ratio of 2:1 up    to 1:2, preferably in a ratio of 1.8:1 to 1:1.8, more preferably in    a ratio of 1.5:1 up to 1:1.5, most preferably in a ratio of 1.2:1 up    to 1:1.2.

-   45. Combination for production of rigid or flexible foams,    comprising at least one component A and component B, where component    A comprises at least one hydroxy-functionalized polymer according to    any of the preceding embodiments and at least one    metal-siloxane-silanol(ate) compound according to any of the    preceding embodiments, and component B comprises at least one    compound having one or more isocyanate groups according to any of    the preceding embodiments, characterized in that components A and B    are each present separately and in a relative ratio of 2:1 up to    1:2, preferably in a ratio of 1.8:1 to 1:1.8, more preferably in a    ratio of 1.5:1 up to 1:1.5, most preferably in a ratio of 1.2:1 up    to 1:1.2.

-   46. Unfoamed polyurethanes producible by a process using at least    one metal-siloxane-silanol(ate) compound according to one or more of    Embodiments 20 to 25.

-   47. Unfoamed polyurethanes according to Embodiment 46, characterized    in that they are elastomers.

-   48. Unfoamed polyurethanes according to Embodiment 47, characterized    in that they are thermosets.

-   49. Unfoamed polyurethanes according to Embodiments 46 to 48,    characterized in that they have a density in the range according to    DIN EN ISO 845:2009-10 of 800 to 1950 kg/m³, preferably in the range    from 950 to 1750 kg/m³, more preferably in the range from 980 to    1650 kg/m³, most preferably in the range from 990 to 1600 kg/m³.

-   50. Unfoamed polyurethanes according to Embodiments 46 to 49,    characterized in that they have a Shore 00 hardness according to    ASTM D2240-15 in the range of 40-100, preferably in the range from    45 to 95, preferably in the range from 50 to 90, especially    preferably in the range from 55 to 85.

-   51. Unfoamed polyurethanes according to Embodiments 46 to 50,    characterized in that they have a Shore A hardness according to ASTM    D2240-15 in the range of 0-100, preferably in the range from 5 to    95, preferably in the range from 10 to 90, especially preferably in    the range from 15 to 85.

-   52. Unfoamed polyurethanes according to Embodiments 46 to 51,    characterized in that they have a Shore D hardness according to ASTM    D2240-15 in the range of 0-100, preferably in the range from 5 to    95, preferably in the range from 10 to 90, especially preferably in    the range from 15 to 85.

-   53. Flexible foams producible by a process using at least one    metal-siloxane-silanol(ate) compound according to one or more of    Embodiments 20 to 25.

-   54. Flexible foams according to Embodiment 53, characterized in that    they have a Shore A hardness according to ASTM D2240-15 of ≥20.

-   55. Flexible foams according to Embodiment 53 or 54, characterized    in that they have a Shore A hardness according to ASTM D2240-15    between 20 and 100, preferably between 20 and 60, more preferably    between 20 and 50.

-   56. Flexible foams according to embodiment 53, 54 or 55,    characterized in that they have a tensile strength according to DIN    EN ISO 1798:2008-04 of ≥200 kPa.

-   57. Flexible foams according to embodiment 53, 54 or 55,    characterized in that they have a tensile strength according to DIN    EN ISO 1798:2008-04 between 200 and 350 kPa.

-   58. Rigid foams producible by a process using at least one    metal-siloxane-silanol(ate) compound according to one or more of    Embodiments 20 to 25.

-   59. Rigid foams according to Embodiment 58, characterized in that    the rigid foams are produced by the process according to Embodiment    43.

-   60. Rigid foams according to embodiment 58 or 59, characterized in    that they have a tensile strength according to ISO 1926:2009-12 of    ≥100 kPa.

-   61. Rigid foams according to embodiment 51, 52 or 53, characterized    in that they have a tensile strength according to ISO 1926:2009-12    between 200 and 2000 kPa.

-   62. Use of at least one metal-siloxane-silanol(ate) compound for    production of flexible foams for use in CASE applications (coatings,    adhesives, sealants and elastomers) and/or elastomer materials.

-   63. Use of at least one metal-siloxane-silanol(ate) compound for    production of flexible foams in furniture, mattresses, car seats,    seal materials or acoustic materials.

-   64. Use of at least one metal-siloxane-silanol(ate) compound for    production of rigid foams in sound insulations, heat insulations    and/or cold insulations, or in CASE applications (coatings,    adhesives, sealants and elastomers).

-   65. Use of at least one metal-siloxane-silanol(ate) compound for    production of rigid foams for insulation of district heating pipes,    tanks and pipelines, and for production of all kinds of    refrigeration units.

-   66. Use of at least one metal-siloxane-silanol(ate) for production    of rigid foams in insulation panels for the fields of use of roofs,    walls, floors and/or ceilings, in window frame insulations or as    assembly foam.

EXAMPLES Example I)—Unfoamed Polyurethanes

The comparative examples (EP1-EP18) show the influence of the gelcatalyst according to the invention. In spite of the influence of acertain water content, it is possible to produce even unfoamedpolyurethanes at a high technical level. The known blowing catalystsDBTL and DABCO that are utilized in the specialist field show muchpoorer performance in direct comparison. It has thus been found that,surprisingly, metal-siloxane-silanol(ate) compounds catalyse the gelreaction particularly selectively.

In the course of the studies, it has been found that, surprisingly, theuse of TiPOSS as catalyst for the construction of unfoamed polyurethanesystems catalyses the gel reaction particularly selectively, withconsiderable differences from the DBTL and TEDA reference gel catalyststested by comparison. In the context of this study, polyol mixtures(components A) each having equal proportions of catalyst and risingwater contents were produced. Components A obtained by comparison werereacted with polymer MDI (component B) in a stoichiometric ratio to givepolyurethane compounds. The assessment of the reactions involved in thecuring process (gel and blowing reaction) was made with reference to thedensity and hardness values obtained, and the foaming characteristics.

The following materials were used for the production of component A, ofcomponent B and of the elastomer products (EP):

-   -   Voranate M230, BASF    -   PolyU-Pol M5020 (OH number 35 mg KOH/g, viscosity 850 mPa*s),        PolyU GmbH    -   BNT-Cat 422, dibutyltin dilaurate (DBTL), 20% and 1% strength,        dissolved in Hexamoll® DINCH, BASF    -   Heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS)    -   TiPOSS, 20% and 1% strength, dissolved in Hexamoll® DINCH, BASF    -   Dabco® 33 LV, 1,4-diazabicyclo[2.2.2]octane, also        triethylenediamine (DABCO or TEDA), 33% strength in dipropylene        glycol, Evonik

A-I) Production of Components A—Comparative Examples to Study theInfluence of Different Water Contents:

In one reaction vessel each, the comparative examples of component Awere produced by adding 0.1% (A4-A6), 0.2% (A7-A9), 0.4% (A10-A12), 0.6%(A13-A15) and 0.8% (A16-A18) of water to an initial charge of 200 g ofPolyU-Pol M5020 and mixing with a propeller stirrer at 2500 min⁻¹. Foreach mixture of different water content, after being left to stand for 1h, the batches were divided into 3×60 g batches, and 1% of a 20% TiPOSSsolution in DINCH, 1% of a 20% DBTL solution in DINCH and 0.66% of a 33%TEDA solution in dipropylene glycol were added, and they were mixed onceagain at 2500 min⁻¹ for 1 min. In addition, as reference materials,mixtures (A1-A3) were produced without additional introduction of water.

TABLE 3 Composition of components B B1-B18 for the study A1 A2 A3 A4 A5A6 A7 A8 A9 PolyU- 100 100 100 100 100 100 100 100 100 Pol M5020 TiPOSS1 — — 1 — — 1 — — 20% in DINCH DBTL — 1 — — 1 — — 1 — 20% in DINCH TEDA— — 0.66 — — 0.66 — — 0.66 33% in DPG Water 0 0 0 0.1 0.1 0.1 0.2 0.20.2 B10 B11 B12 B13 B14 B15 B16 B17 B18 PolyU- 100 100 100 100 100 100100 100 100 Pol M5020 TiPOSS 1 — — 1 — — 1 — — 20% in DINCH DBTL — 1 — —1 — — 1 — 20% in DINCH TEDA — — 0.66 — — 0.66 — — 0.66 33% in DPG Water0.4 0.4 0.4 0.6 0.6 0.6 0.8 0.8 0.8

B-I) Reaction of Components A A1 to A18 with Polymer MDI, Voranate M230(Component B)

In a disposable beaker, Voranate M230 (component B) was added to 20 g ineach case of the mixtures A1-A18 produced in 1) in a stoichiometricratio (100% isocyanate conversion based on the resulting overall OHnumber of the polyol mixture), and the mixture was mixed with apropeller stirrer at 1500 min⁻¹ for 10 s. 15 g of the mixture was thentransferred to a 100 ml PP beaker, and the curing characteristics weredetermined with reference to foaming characteristics, density and ShoreA hardness of the resultant elastomer products EP1-EP18 (numbering as inthe table above). The results can be found in Table 4 below.

C-I) Results of the Syntheses of the Elastomer Products (EP)

The visual assessment of the foaming characteristics of the variouselastomer products EP1-EP18 shows that the TiPOSS-catalysed combinations(comprising components A and B) (marked area of the table, EP1, EP4,EP7, EP10, EP13 and EP16) foam only at a greater water content (EP16,water content about 0.8%) than the correspondingly DBTL- orTEDA-catalysed mixtures (EP11 and EP12, water content about 0.4%). FIGS.1-5 show the foaming characteristics with increasing water content andthe surprising effect of TiPOSS catalysis in the reaction of component Awith component B.

Example II)—Foamed Polyurethanes Example IIa)—Flexible Foams

It has been found that, surprisingly, the use of TiPOSS as catalyst forthe production of foamed polyurethane systems leads to products having aconsiderable improvement in the level of strength compared to foamedpolyurethane systems that are obtained via conventional catalysis. Theincrease in strength is advantageous since the polyurethane foamsproduced with TiPOSS can withstand greater mechanical loads.

The study of the catalytic properties of TiPOSS in foamed polyurethanesystems was conducted on 2-component polyurethane reaction mixtures (Acomponent=multicomponent system with base polyol, Bcomponent=isocyanate) that find use, for example, for production ofgaskets foamed in situ in a component (formed-in-place foam gasket,FIPFG). In this process, the 2-component reaction mixture is applieddirectly to the component in as yet unreacted form with the aid of a CNCmachine or a robot.

For the study, significantly simplified base formulations were used,which are guided in their raw material setup by the above-described2-component reaction systems for the FIPFG process. The raw materialsused are listed in Table 5 below. The assessment of TiPOSS as catalystfor the foam-forming process was made by producing the foams

-   -   either with just one catalyst (TiPOSS or DBTL or TEDA/DABCO)    -   or with a catalyst mixture (TiPOSS and TEDA or DBTL and        TEDA/DABCO).

TABLE 5 Base constituents of the A component for the production offoamed polyurethane systems PolyU-Pol M5020 Base polyol, EO-tippedpolyether triol, M~4850 g/mol Glycerol, Alfa Aesar Crosslinker WaterBlowing agent Catalyst 1 Metal catalyst, TiPOSS Catalyst 2 Metalcatalyst, DBTL Catalyst 3 Amine catalyst, TEDA

The reactions were conducted at various indices (index 100 meanscomplete conversion of the A component (OH) with the B component (NCO);index 75 and index 50 mean 25% and 50% NCO deficiency respectively),since the production of industrially produced gasket foams in this indexrange is common practice and is used for adjusting foam properties suchas hardness, density, strength properties and compressioncharacteristics.

A-IIa) Production of Gasket Foams (GF) GF1-GF15:

Production of the A Component:

For the production of the A components, 5×500 g batches were producedwith the percentage ratios specified in Table 6 below. For this purpose,an initial charge of PolyU-Pol M5020, glycerol and water was admixedwith the amounts, specified in Table 6, of a 20% TiPOSS solution inDINCH (for GF1, GF6 and GF11), a 20% DBTL solution in DINCH (for GF2,GF7 and GF12), a 33% TEDA solution in dipropylene glycol (for GF3, GF8and GF13), a mixture of a 20% TiPOSS solution in DINCH with a 33% TEDAsolution in dipropylene glycol (for GF4, GF9 and GF14), a mixture of a20% DBTL solution in DINCH and 0.66% of a 33% TEDA solution indipropylene glycol (for GF5, GF10 and GF15) and mixed with a propellerstirrer at 2500 rpm.

BIIa) Reaction of the A Component with the B Component Polymer MDI,Voranate M230

In a 300 ml disposable beaker, 80-140 g of the A component in each casewas prepared with the appropriate amount of the B component (PMDIisocyanate, Voranate M230) apparent from the mixing ratio in the MR linein Table 6 below, and mixed with a propeller stirrer at 2500 rpm for 15s. The different mixing ratios MR represent the degree of conversion ofthe A component with the B component (index 100, index 75 and index 50).

Columns GF1-GF5, MR 3.8:1 to MR 3.9:1 correspond to 100% conversion ofthe A component with the B component (stoichiometric conversion NCO:OH)

Columns GF6-GF10, MR 5.2:1 to MR 5.1:1 correspond to 75% conversion ofthe A component with the B component (B component is present indeficiency)

Columns GF11-GF15, MR 7.7:1 to MR 7.6:1 correspond to 50% conversion ofthe A component with the B component (B component is present indeficiency) The mixtures of A and B components (about 90-150 g) werepoured into an open plastic mould (Ø 20 cm, t=1 cm), demoulded and curedat 23° C. for 72 h.

C-IIa) Results of Gasket Foam Investigations GF1-GF15

The resultant foam slabs (h˜1 cm) GF1-GF15 were used to ascertain thetechnical properties such as density, Shore A hardness, tensilestrength, elongation at break and compression set. The results can befound in Table 6 below.

D-IIa) Conclusion

The mixture experiments GF1-GF15 gave foams having a smooth surface andfine cell structure. Comparison of the technical parameters of thegasket foams GF1 to GF5 for index 100 (stoichiometric conversion, markedarea) makes it clear that tensile strength TS is significantly elevatedfor TiPOSS-catalysed systems in particular (GF1 compared to GF2 and GF3,and GF4 compared to GF5). This observation is reflected analogously inthe systems that were produced with a deficiency of isocyanate (forindex 75 GF6 compared to GF7 and GF8, and GF9 compared to GF10, andindex 50 GF11 compared to GF12 and GF13, and GF14 compared to GF15).

The essential outcome of the experiments can be summarized in that theuse of TiPOSS as catalyst leads to more selective formation ofpolyurethane linkages and hence to improved strength properties in thefoam systems examined.

Example IIb)—Rigid Foams

The study of the catalytic properties of TiPOSS in rigid polyurethanesystems was conducted on 2-component polyurethane reaction mixtures (Acomponent=multicomponent system with polyols of low molecular weight andrelatively high functionality, B component=isocyanate), which find use,for example, in the production of seals, fillings and insulations ofgaps/cavities in housing components of electronic devices (e.g. whitegoods).

The study took place—in analogy to the above studies—using a greatlysimplified base formulation that was guided in its raw materialselection by the above-described 2-component reaction systems for thefilling of cavities with foam. The raw materials used are listed inTable 7 below.

TABLE 7 Base constituents of the A component for the production of arigid polyurethane foam system PolyU-Pol G500 Polyether polyol, MW = 560g/mol, OH functionality ~3, PolyU GmbH PolyU-Pol Polyether polyol, MW =600 g/mol, OH functionality ~4.5, PolyU GmbH RF551 Water Blowing agentCatalyst 1 Metal catalyst, TiPOSS Catalyst 2 Amine catalyst, Dabco 33LV, TEDA (triethylenediamine 33% in DPG), Evonik Catalyst 3 Blowingcatalyst, Dabco DMDEE (2,2′-dimorpholinediethyl ester), EvonikStabilizer Tegostab B 8863z, Evonik

The assessment of TiPOSS as catalyst for the rigid foam-forming processwas made by producing

-   -   rigid foam 1 (RF1) with a catalyst mixture of Dabco DMDEE        (blowing catalyst) and TiPOSS (gel catalyst) and    -   rigid foam 2 (RF2) with a catalyst mixture of Dabco DMDEE        (blowing catalyst) and Dabco 33 LV (gel catalyst).

The reactions were conducted at index 100, i.e. full conversion of the Acomponent (OH) with the B component (NCO).

A-IIb) Production of the Rigid Foams (RF) RF1 and RF2:

Density

Production of the A Component:

For the production of the A components, 2×500 g batches were producedwith the percentage ratios specified in the table below. For thispurpose, PolyU-Pol G500, PolyU-Pol RF551, DMDEE, water and Tegostab B8863z were initially charged and admixed with the amounts, specified inthe table, of a 20% TiPOSS solution in DINCH (RF1) and a 33% TEDAsolution in dipropylene glycol (RF2), and mixed with a propeller stirrerat 2500 rpm for 2 min.

Reaction of the A Component with the B Component Polymer MDI, VoranateM230

In an 800 ml disposable beaker, 300 g of the A component in each casewas prepared with the appropriate amount (˜275 g) of the B component(PMDI isocyanate, Voranate M230, BASF) apparent from the mixing ratio inthe MR line in Table 8 below, and mixed with a propeller stirrer at 2500rpm for 15 s.

The mixtures of A and B components (about 550 g) were poured into aplastic-lined wooden box (20 cm×20 cm×23 cm), cured at 23° C. for 72 hand demoulded.

B-IIb) Results of the Rigid Foam Studies RF1 and RF2

The requisite test specimens were sawn out of the rigid foam cubesobtained (20 cm×20 cm×˜14 cm, RF1 and RF2) by means of a bandsaw, andthese were used to ascertain the technical properties such as density,Shore D hardness (surface measurement), tensile strength and elongationat break. The results of the studies can be found in Table 8 below.

C-IIb) Conclusion

In both cases, mixture experiments RF1 and RF2 gave rigid foams having avery smooth surface. The foam structure in the foams RF1 and RF2examined is a fine-cell structure overall, and tends to have finer cellsthan the foam obtained with TiPOSS. Comparison of the technicalparameters of the gasket foams RF1 and RF2 makes it clear that tensilestrength TS is improved for the TiPOSS-catalysed system (RF1 compared toRF2, marked area). By contrast, the other parameters (density andhardness) remain constant.

The essential outcome of the experiments can be summarized in that theuse of TiPOSS as catalyst can be utilized in rigid foam systems as wellfor selective formation of polyurethane linkages and hence for improvedstrength properties in the foam systems examined.

Example III)—Procedure for Ascertaining Selectivity (According toFarkas)

For determination of the selectivity (“gel/blow reaction selectivity”)of catalysts in the production of polyurethanes by means of thetitration method according to Farkas, an aliquot of 50 ml of a tolylene2,4-diisocyanate (TDI)-benzene solution (0.1533 mol/l) and an aliquot of50 ml of a diethylene glycol- (DEG, 0.1533 mol/l) or water-benzenesolution (0.0752 mol/l) was reacted with 5 ml of a catalyst-containingbenzene solution (0.0735 mol/l) at 30-70° C. At various time intervals,a sample was taken from the reaction flask, and the unreacted isocyanatewas quenched with the n-butylamine-benzene solution. The NCO content ofthe respective sample was determined by back-titration with astandardized HCl solution.

In the titration method, it is assumed that the reaction of isocyanatewith diol (or with water) in the presence of a catalyst is a first-orderreaction in relation to the isocyanate or alcohol concentration.

$\begin{matrix}{\frac{dx}{dt} = {K\left( {a - x} \right)}^{2}} & (A)\end{matrix}$

in whichx is the concentration of NCO groups converted,a is the initial concentration of the NCO groups,K is the reaction rate constant (I/mol/h), andt is the reaction time (h).

The integration of equation (A), introducing the initial state (x=0 whent=0), gives the following expression:

$\begin{matrix}{\frac{1}{a - x} = {{Kt} + \frac{1}{a}}} & (B)\end{matrix}$

The catalysis reaction constant Kc can be obtained for any catalystassuming equation (C):

K=K ₀ +Kc×C  (C)

in whichK₀ is the reaction rate constant (I/mol h, no catalyst),Kc is the catalysis reaction constant (I²/eq mol h), andC is the concentration of the catalyst (mol/l).

The activities of the gel and blow reactions, ascertained by thetitration method in the model reaction of TDI/DEG (or water), is shownin Table A for a selection of prior art catalysts.

TABLE A Activities of the gel and blow reactions, and selectivity of thecatalysts ascertained via titration method Activity of Activity of thegel the blow reaction reaction Selectivity k1w k2w (gel reaction/Abbreviation Chemical name (×10) (×10) blow reaction) TEA Triethylamine1.16 0.60 1.93 DMCHA Dimethylcyclohexylamine 2.22 0.83 2.67 TETetramethylethylenediamine 4.19 1.14 3.68 MRTetramethylhexamethylenediamine 2.95 0.84 3.51 DTPentamethyldiethylenetriamine 4.26 15.9 0.27 PMAPentamethyldipropylenetriamine 3.80 1.16 3.28 TEDA or Triethylenediamine10.9 1.45 7.52 DABCO DMP Dimethylpiperazine 1.3 0.28 4.64 NPDimethylaminoethylmethylpiperazine 1.71 0.78 2.19 NEM N-Ethylmorpholine0.22 0.01 22.00 TRC Tri(dimethylaminopropyl)hexahydro- 3.00 1.12 2.681,3,5-triazine ETS Bis(2-Dimethylaminoethyl) ether 2.99 11.7 0.26 DMEADimethylaminoethanol 2.91 0.36 8.08 HP Hydroxyethylmethylpiperazine 0.610.11 5.55 RX3 Dimethylaminoethoxyethanol 1.84 2.55 0.72 RX5Trimethylaminoethylethanolamine 2.89 4.33 0.67 F22 Special catalyst forCASE 26.1 0.83 31.45 applications DBTL Dibutyltin dilaurate 14.4 0.4830.00

Example IV

The present invention also relates to a composition and to a process forproducing polyurethane prepolymers and polyurethane systems based onpolyols, di- or polyisocyanates and a TiPOSS-based catalyst.

TiPOSS-based catalysts that are preferred in accordance with theinvention are those disclosed in EP 2 989 155 B1 and EP 2 796 493 A1.The disclosure of these documents is fully incorporated with regard tothe catalysts. Particular preference is given to the catalysts(metallosilsesquioxane) according to claim 5 of EP 2 989 155 B1.

The study of the activity of heptaisobutyl POSS-titanium(IV) ethoxide(TiPOSS) for the formation of polyurethane compounds was conducted byway of example in comparison with dibutyltin dilaurate (DBTDL) andtin(II) 2-ethylhexanoate (tin octoate) in various unfoamed and foamedpolyurethane systems. Particular attention was paid to the effect on thepreparation of the silylated polyurethanes (SPUR) by the IPDI route. Themodel formulations from the CASE application sectors, soft foam andflexible foam (slabstock foam), were examined here with regard to theircuring characteristics at room temperature (23° C./50% RH) using variouspolyols and isocyanates with the same catalyst content of TiPOSS andDBTDL or tin octoate. For simplification, the studies have beenconducted under the assumption that a complete stoichiometric reaction(index 100) can take place between isocyanate and polyol. In principle,the studies are also applicable to the preparation of prepolymers. Thecatalytic activity of the catalysts examined was determined by thedetermination and comparison of cream time, fibre time and tack-freetime.

1.) Study of TiPOSS/DBTDL in Unfoamed Polyurethane Formulations

a) Propylene Glycol Polyols

The polyol A component consisted of a polypropylene diol and the TiPOSScatalyst in the form of a 20% solution in diisononyl phthalate (DINP).For comparison of catalytic activity, a corresponding identical polyol Acomponent was prepared using DBTDL. The amount of catalyst was 0.2 percent by weight in each case (neglecting the amount of solvent). In orderto study the influence of molecular weight, the molecular weight wasadditionally varied from low (MW ˜2000) to high (MW ˜18 000), since itcan be assumed that the reactivity of polypropylene polyols that are oflimited reactivity in any case will decrease further with risingmolecular weight, and hence differences in reactivity will beparticularly readily observable.

The polypropylene polyols tested were accordingly those with MW˜2000(Rokopol D2002, PCC Rokita), MW ˜8000 (Rokopol LDB 8000), MW ˜12 000(Rokopol LDB 12 000) and MW ˜18 000 (Rokopol LDB 18 000).

The crosslinker components used were the isocyanates P-MDI (VoranateM230, Dow), IPDI (Wanate IPDI, DKSH) and HDI trimer isocyanurates(Vestanat HT2500/100). The reaction between polyol A and isocyanate Bcomponent was effected by stirring the two components at 1000 rpm with aconventional propeller stirrer for 10 s. After the stirring process hadended, the resultant reaction mixture was cast into slabs of thickness˜6 mm (10 g). The curing characteristics were determined from the creamtime, fibre time and tack-free time.

It was found that the TiPOSS-catalysed curing of polyurethane at roomtemperature is significantly accelerated using the polypropylene polyolsdescribed compared to the corresponding DBTDL-catalysed crosslinking.The acceleration of the reaction, according to the combination of polyoland isocyanate examined, is between a factor of 2 and a factor of 100.Viewed overall, the factor of reaction acceleration when TiPOSS is usedparticularly surprisingly increases for the HDI trimer of isocyanurateused, and to a lesser degree for IPDI.

Conclusion for SPUR Methodology:

Since the reaction between the DMC polyols and IPDI isocyanate is thecrucial reaction for the commercial preparation of SPUR (hybridpolymers), this finding is of great significance. Since we are alreadyable to establish a considerable increase in reaction at roomtemperature and with 1:1 stoichiometry, it can be expected that, underthe customary conditions of SPUR prepolymer preparation, it is possibleto work with considerably smaller amounts of catalyst (1/5 to 1/10)and/or a lower temperature (<80° C.) and/or shortening of the reactiontime. Since the formation of by-products in this preparation leads to anunwanted increase in viscosity, a distinct improvement in the reactionregime and product quality is thus to be expected.

With regard to the ever-increasing economic significance of the SPURproducts, the use of the TiPOSS catalyst is expected to lead both to acost benefit over tin catalysts and to a product benefit.

a) Propylene Glycol Polyols, Ethylene Glycol-Tipped

In order to assess whether these observations are also applicable tomore reactive polyether polyols, by way of example, polyether polyolswith MW ˜4000 and f=2 and MW ˜4850 and f=3 tipped with ethoxy groups atthe termini were examined. It has been found that the differences inreactivity of the polyol systems catalysed with TiPOSS and DBTDL aresmaller in the case of use of reactive polyether triol. Here too, it isagain observed that the acceleration in reactivity of the crosslinkingby TiPOSS is particularly effective for the HDI trimer.

2.) Study of the Activity of TiPOSS/DBTL in Silane-TerminatedPolyurethanes

The speed of fibre formation and curing in silane-terminatedpolyurethanes was determined on 6 mm SPUR slabs that had been producedby mixing the silane-terminated polyurethanes with 0.2 per cent byweight each of TiPOSS and DBTL (each in solution, 20% in DINP). Themixing was effected with exclusion of air in an argon inert gasatmosphere with a conventional propeller stirrer. The mixed material wascured at 23° C./50% RH.

3.) Study of the Activity of TiPOSS/DBTDL in Flexible Polyurethane FoamFormulations

The polyol A component consisted of a reactive, ethoxy group-tippedpolyether triol (Rokopol M 5020, f=3), water and the TiPOSS catalyst, inthe form of a 20% solution in diisononyl phthalate (DINP). Forcomparison of catalytic activity, a corresponding identical polyol Acomponent was prepared using DBTDL. The amount of catalyst was 0.2 percent by weight in each case (neglecting the DINP solvent). By way ofcomparison, the reaction was conducted using a less reactivepolypropylene polyol (Rokopol D 2002, f=2).

The crosslinking component used was the isocyanate P-MDI (VoranateM230). The reaction between polyol A and isocyanate B component waseffected by stirring the two components at 2500 rpm with a conventionalpropeller stirrer for 10 s. The reaction was stoichiometric. After thestirring process had ended, the reaction mass obtained (20 g) was pouredinto cups. The curing characteristics were determined from the creamtime and tack-free time.

It was found that the activity of TiPOSS when using ethoxylated polyolsis comparable to that of DBTDL. By contrast, the curing process in thecase of the formulation made from a pure polypropylene polyol is moresignificantly accelerated by TiPOSS.

4.) Study of the Activity of TiPOSS/Tin Octoate in a SlabstockPolyurethane Foam Formulation

The polyol A component consisted of a standard polyester polyol based onDesmophen 2200 B, an amine catalyst (N,N-dimethylpiperazine andN,N-dimethylhexadecylamine), cell stabilizers, water and the TiPOSScatalyst, in the form of a 20% solution in DINP. For comparison ofcatalytic activity, a corresponding identical polyol A component wasprepared using tin octoate. The amount of TiPOSS and tin octoatecatalyst was 0.03 per cent by weight in each case.

The crosslinking component used was the isocyanate Desmodur T65 and aprepolymer having an NCO content of about 12%. The reaction was effectedin a stoichiometric ratio (index 100). The reaction between polyol A andisocyanate B components was effected by stirring the two components at1000 rpm with a Visco Jet stirrer unit for 10 s. After the stirringprocess had ended, the resultant reaction mass (˜400 g) was poured intoa 2 L wooden box, and the curing characteristics were determined fromthe cream time and tack-free time.

It was found that the activity of TiPOSS is comparable to that of tinoctoate. The resultant foams from the reaction with TiPOSS have lowerdensity; strength properties and indentation hardness arecorrespondingly lower.

5.) Overall Conclusion/Applications

a) Use of TiPOSS in the Preparation of SPUR Prepolymers

The significant increase in reaction described in the reaction betweenthe DMC polyols and IPDI can be used for the commercial production ofSPUR (hybrid polymers). It can be expected here that it will be possibleto use considerably smaller amounts of catalyst (1/5 to 1/10) and/or alower temperature (<80° C.) and/or a shortened reaction time. Since, ingeneral, the formation of by-products in this preparation leads to anunwanted increase in viscosity, a distinct improvement in the reactionregime and product quality, including lower product viscosity (veryimportant for the formulator), is thus possible.

b) Preparation of KOH-Based PU Prepolymers with TiPOSS

The formation of prepolymers obtained from the reaction of KOH-basedpolyols and aliphatic and aromatic isocyanates can be brought about withconsiderably smaller amounts of TiPOSS catalyst (1/5 to 1/10) and/or alower temperature (<80° C.) and/or a shortened reaction time. Since theformation of by-products in this preparation leads to an unwantedincrease in viscosity, a distinct improvement in the reaction regime andproduct quality can thus be assumed.

c) Use of TiPOSS in 2-Component Clear Encapsulating Systems and PUVarnishes Based on HDI and Other Aliphatic Isocyanates

Use of TiPOSS as catalyst increases the curing rate in 2-componentpolyurethane clear encapsulation systems and PU varnishes. The increasein molecular weight distinctly improve the mechanical properties of thevarnishes and encapsulating compounds.

d) TDI Foams/Use of TiPOSS in the Production of Slabstock Foams

In the production of TDI-based slabstock foams, through use of TiPOSS ascatalyst, it is possible to dispense with the use of tin compounds thatare harmful to health—as in all other applications mentioned in 5.).There is no loss here in product quality.

e) FIPFG (Foamed in Place Foam Gaskets)—Sealant Foams

The production of 2-component polyurethane systems for the FIPFG processbased on TiPOSS-catalysed curing is particularly advantageous since thecuring process is accelerated by the higher reactivity of TiPOSScompared to DBTL. Polyurethane products can additionally be producedwithout tin compounds that are harmful to health, which is particularlyimportant for the production of sealant materials in the medical sector,kitchen applications, etc.

f) Use of TiPOSS in Moisture-Curing 1-Component Isocyanate-TerminatedPrepolymers

The curing of 1-component isocyanate-terminated prepolymers can beaccelerated by the use of TiPOSS. It is possible to dispense with theuse of tin compounds that are harmful to health. This is of particularrelevance when these prepolymers are used as adhesives for customaryfloor coverings, since it is thus possible to avoid possiblecontamination, even if only by small amounts of tin, via the skin of thefoot.

6.) Specific Embodiments

Studies on the activity of heptaisobutyl-POSS-titanium(IV) ethoxideTiPOSS in comparison to DBTL

TABLE 1 Polyols from the KOH-catalyzed reaction f = 2, MW = 2000, PO f =2, MW = 4000, PO, EO tipped Isocyanate Catalyst f = 3, MW = 4800, PO, EOtipped P-MDI* TiPOSS 0.2% vs. + DTBL 0.2 % P-MDI TiPOSS 0.2% vs. ++ DTBL0.2 %

TABLE 2 SPUR Catalyst activity Silylated TiPOSS 0.2% vs. + PolyurethaneDTBL 0.2 % (nonaromatic)

LIST OF ABBREVIATIONS

Coatings, Adhesives, Sealants, Elastomers (CASE)

Diisononyl phthalate (DINP)

Dibutyltin dilaurate (DBTDL or DBTL)

Tin(II) 2-ethylhexanoate (tin octoate)

Silylated polyurethanes/silylated polyurethane resins (SPUR)

Heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS)

Dimethylcyclosiloxane (DMC)

Polyurethane (PU)

Potassium hydroxide (KOH)

FIPFG (foamed in place foam gaskets—gasket foams)

Titanium (Ti)

Polyhedral oligomeric silsesquioxane (POSS)

EMBODIMENTS, ESPECIALLY FOR EXAMPLES IV

-   1. Process for preparing prepolymers by reacting a component A with    a component B in the presence of a catalyst in a liquid medium,    where component A is a polyol and component B a crosslinking    component (crosslinker), characterized in that component A is in    deficiency relative to component B, and component A and component B    are especially used in a ratio of at least 1:1.05, preferably of    1:2.2, and the catalyst is selected from the group of the tin-free    polyhedral oligomeric metallosilsesquioxanes, preferably from the    group of the titanium(IV) polyoctahedral silsesquioxanes.-   2. Process for preparing polyurethanes by combining a two-component    system having a component A and a components B in the presence of a    catalyst in a liquid medium, where component A is a polyol and    component B a crosslinking component (crosslinker), characterized in    that components A and B are present separately, and the catalyst has    preferably been formulated with component A, and components A and B    are present in a ratio of 1.2:1.0 up to 1.0:1.2.-   3. Process for producing polyurethane systems, characterized in that    the prepolymers are prepared or preparable according to either of    Embodiments 1 and 2 using a catalyst selected from the group of the    tin-free polyhedral oligomeric metallosilsesquioxanes, preferably    from the group of the titanium(IV) polyoctahedral silsesquioxanes.-   4. Process according to Embodiment 3, characterized in that the    prepolymers are functionalized before the reaction with    aminosilanes.-   5. Process according to any of the preceding embodiments,    characterized in that auxiliaries are added.-   6. Process according to Embodiment 5, characterized in that the    auxiliaries are selected from the group consisting of water, cell    stabilizers, amine catalysts, fillers, adhesion promoters, moisture    scavengers, plasticizers, UV stabilizers, thixotropic agents, or    combinations thereof, preferably with one or more additives being    one or more silanes.-   7. Process according to Embodiment 6, characterized in that the    amine catalyst may be N,N-dimethylpiperazine and/or    N,N-dimethylhexadecylamine or a mixture thereof.-   8. Process according to any of the preceding embodiments,    characterized in that the catalyst is R¹—POSS-titanium(IV) ethoxide    (TiPOSS) where R¹ is an alkyl, allyl or aryl radical or mixtures    thereof, and R¹ is preferably a heptaisobutyl radical.-   9. Process according to any of the preceding embodiments,    characterized in that the catalyst content is between 0.0001% and 5%    by weight, preferably between 0.001% and 2% by weight, further    preferably between 0.01% and 0.3% by weight, especially preferably    0.2, more especially preferably 0.03.-   10. Process according to any of the preceding embodiments,    characterized in that the crosslinker is an isocyanate.-   11. Process according to Embodiment 10, characterized in that the    isocyanate is aromatic and/or aliphatic, preferably methylene    diphenyl isocyanates (MDI) and/or isophorone diisocyanate (IPDI)    and/or a hexamethylene diisocyanate trimer (HDI trimer) or a mixture    thereof.-   12. Process according to any of the preceding embodiments,    characterized in that the polyol is a polyoxypropylene diol,    preferably having a molar mass between 2000 g/mol and 18 000 g/mol,    more preferably having a molar mass between 12 000 g/mol and 18 000    g/mol.-   13. Process according to any of the preceding Embodiments 1 to 11,    characterized in that the polyol is an ethoxylated polyol,    preferably a polyether triol tipped with ethoxy groups, and more    preferably has a molar mass between 2000 g/mol and 4850 g/mol.-   14. Process according to any of Embodiments 1 to 11, characterized    in that the polyol is a polyester polyol, preferably Desmophen 2200    B.-   15. Process according to any of the preceding embodiments,    characterized in that the polyol comes from a KOH— and/or    DMC-catalysed reaction.-   16. Process according to any of the preceding embodiments,    characterized in that the liquid medium is an organic solvent,    preferably diisononyl phthalate (DINP).-   17. Process according to any of the preceding embodiments,    characterized in that it is tin-free.

1. A composition comprising at least one silylated polymer (SiP) and atleast two catalysts A and B, wherein catalyst A is ametal-siloxane-silanol(ate) compound.
 2. The composition according toclaim 1, wherein catalyst A is heptaisobutyl POSS-titanium(IV) ethoxide(TiPOSS), and catalyst B is a metal-siloxane-silanol(ate) compound. 3.The composition according to claim 2, wherein catalyst A isheptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS), and catalyst B isheptaisobutyl POSS-tin(IV) ethoxide (SnPOSS).
 4. The compositionaccording to claim 1, wherein catalyst B is not ametal-siloxane-silanol(ate) compound.
 5. The composition according toclaim 4, wherein catalyst B is an organometallic compound.
 6. Thecomposition according to claim 4, wherein catalyst B is selected fromthe group consisting of tetraalkyl titanates, such as tetramethyltitanate, tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyltitanate, tetra-n-butyl titanate, tetraisobutyl titanate,tetra-sec-butyl titanate, tetraoctyl titanate, tetra(2-ethylhexyl)titanate, dialkyl titanates ((RO)₂TiO₂ in which R is, for example,isopropyl, n-butyl, isobutyl), such as isopropyl n-butyl titanate;titanium acetylacetonate chelates, such asdiisopropoxybis(acetylacetonate) titanate,diisopropoxybis(ethylacetylacetonate) titanate,di-n-butylbis(acetylacetonate) titanate,di-n-butylbis(ethylacetoacetate) titanate,triisopropoxidebis(acetylacetonate) titanate, zirconium tetraalkoxides,such as zirconium tetraethoxide, zirconium tetrabutoxide, zirconiumtetrabutyrate, zirconium tetrapropoxide, zirconium carboxylates, such aszirconium diacetate; zirconium acetylacetonate chelates, such aszirconium tetra(acetylacetonate), tributoxyzirconium acetylacetonate,dibutoxyzirconium bisacetylacetonate, aluminium trisalkoxides, such asaluminium triisopropoxide, aluminium trisbutoxide; aluminiumacetylacetonate chelates, such as aluminium tris(acetylacetonate) andaluminium tris(ethylacetylacetonate), organotin compounds such asdibutyltin dilaurate (DBTL), dibutyltin maleate, dibutyltin diacetate,tin(II) 2-ethylhexanoate (tin octoate), tin naphthenate, dimethyltindineodecanoate, dioctyltin dineodecanoate, dimethyltin dioleate,dioctyltin dilaurate, dimethyl mercaptides, dibutyl mercaptides, dioctylmercaptides, dibutyltin dithioglycolate, dioctyltin glycolate,dimethyltin glycolates, a solution of dibutyltin oxide, reactionproducts of zinc salts and organic carboxylic acids (carboxylates) suchas zinc(II) 2-ethylhexanoate or zinc(II) neodecanoate, mixtures ofbismuth carboxylates and zinc carboxylates, reaction products of bismuthsalts and organic carboxylic acids, such as bismuth(III)tris(2-ethylhexanoate) and bismuth(III) tris(neodecanoate) and bismuthcomplexes, organolead compounds such as lead octoxide, organovanadiumcompounds, amine compounds such as butylamine, octylamine, dibutylamine,monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine,oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine,xylylenediamine, triethylenediamine, guanidine, diphenylguanidine,2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine,2-ethyl-4-methylimidazole and 1,8-diazabicyclo(5.4.0)undecene-7 (DBU),salts of these amines with carboxylic acids or other acids or mixturesthereof.
 7. The composition according to claim 6, wherein catalyst B isselected from the group consisting of dibutyltin dilaurate (DBTL),tin(II) 2-ethylhexanoate (tin octoate), zinc(II) 2-ethylhexanoate,zinc(II) neodecanoate, bismuth(III) tris(2-ethylhexanoate), bismuth(III)tris(neodecanoate) or mixtures thereof.
 8. The composition according toclaim 6, wherein catalyst B is dibutyltin dilaurate (DBTL).
 9. Thecomposition according to claim 3, wherein catalyst A is selected fromthe group consisting of heptaisobutyl POSS-titanium(IV) ethoxide(TiPOSS) and heptaisobutyl POSS-tin(IV) ethoxide (SnPOSS), preferably inthat the catalyst is heptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS).10. The composition according to claim 9, wherein said compositionincludes more than one catalyst A metal-siloxane-silanol(ate) compound.11. The composition according to claim 1, wherein themetal-siloxane-silanol(ate) compound has the general formula R*qSirOsMtwhere each R* is independently selected from the group consisting ofoptionally substituted C1- to C20-alkyl, optionally substituted C3- toC6-cycloalkyl, optionally substituted C2- to C20-alkenyl, optionallysubstituted C6- to C10-aryl, —OH and —O—(C1- to C10-alkyl), each M isindependently selected from the group consisting of s- and p-blockmetals, d- and f-block transition metals, lanthanide and actinide metalsand semimetals, especially from the group consisting of metals oftransition groups 1, 2, 3, 4, 5, 8, 10 and 11 and metals of main groups1, 2, 3, 4 and 5, preferably from the group consisting of Na, Zn, Sc,Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably fromthe group consisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, q is aninteger from 4 to 19, r is an integer from 4 to 10, s is an integer from8 to 30, and t is an integer from 1 to
 8. 12. The composition accordingto claim 1, wherein the metal-siloxane-silanol(ate) compound has ageneral structure (I)

where X¹, X² and X³ are independently selected from Si and M¹, where M¹is selected from the group consisting of s- and p-block metals, d- andf-block transition metals, lanthanide and actinide metals andsemimetals, especially from the group consisting of metals of transitiongroups 1, 2, 3, 4, 5, 8, 10 and 11 and metals of main groups 1, 2, 3, 4and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr,Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the groupconsisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, Z¹, Z² and Z³ areindependently selected from the group consisting of L², R⁵, R⁶ and R⁷,where L² is selected from the group consisting of —OH and —O—(C1- toC10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- to C6-alkyl), orwhere L² is selected from the group consisting of —OH, —O-methyl,—O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and —O-isobutyl;R¹, R², R³, R⁴, R⁵, R⁶ and R⁷ are independently selected from the groupconsisting of optionally substituted C1- to C20-alkyl, optionallysubstituted C3- to C8-cycloalkyl, optionally substituted C2- toC20-alkenyl and optionally substituted C5- to C10-aryl; Y¹ and Y² areindependently —O-M²-L³ _(Δ), or Y¹ and Y² are associated and togetherare —O-M²(L³ _(Δ))-O— or —O—, where L³ is selected from the groupconsisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- toC8-alkyl) or —O—(C1- to C6-alkyl), or where L³ is selected from thegroup consisting of —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl,—O-octyl, —O-isopropyl, and —O-isobutyl, and where M² is selected fromthe group consisting of s- and p-block metals, d- and f-block transitionmetals, lanthanide and actinide metals and semimetals, especially fromthe group consisting of metals of transition groups 1, 2, 3, 4, 5, 8, 10and 11 and metals of main groups 1, 2, 3, 4 and 5, preferably from thegroup consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Snand Bi; especially preferably from the group consisting of Zn, Ti, Zr,Hf, V, Fe, Sn and Bi, and X⁴ is -M³L¹ _(Δ) or M³ and Q¹ and Q² are H oreach is a single bond joined to M³, where L¹ is selected from the groupconsisting of —OH and —O—(C1- to C10-alkyl), especially —O—(C1- toC8-alkyl) or —O—(C1- to C6-alkyl), or where L¹ is selected from thegroup consisting of —OH, —O— methyl, —O-ethyl, —O-propyl, —O-butyl,—O-octyl, —O-isopropyl, and —O-isobutyl, and where M³ is selected fromthe group consisting of s- and p-block metals, d- and f-block transitionmetals, lanthanide and actinide metals and semimetals, especially fromthe group consisting of metals of transition groups 1, 2, 3, 4, 5, 8, 10and 11 and metals of main groups 1, 2, 3, 4 and 5, preferably from thegroup consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Snand Bi; especially preferably from the group consisting of Zn, Ti, Zr,Hf, V, Fe, Sn and Bi, or X⁴ is -M³L¹ _(Δ) and Q² is H or a single bondjoined to M³ and Q¹ is H, M⁴L⁴ _(Δ) or where M⁴ is selected from thegroup consisting of s- and p-block metals, d- and f-block transitionmetals, lanthanide and actinide metals and semimetals, especially fromthe group consisting of metals of transition groups 1, 2, 3, 4, 5, 8, 10and 11 and metals of main groups 1, 2, 3, 4 and 5, preferably from thegroup consisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Snand Bi; especially preferably from the group consisting of Zn, Ti, Zr,Hf, V, Fe, Sn and Bi, and where L⁴ is selected from the group consistingof —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or—O—(C1- to C6-alkyl), or where L⁴ is selected from the group consistingof —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl,—O-isopropyl, and —O— isobutyl, and where R⁸ is selected from the groupconsisting of optionally substituted C1- to C20-alkyl, optionallysubstituted C3- to C8-cycloalkyl, optionally substituted C2- toC20-alkenyl and optionally substituted C5- to C10-aryl, or X⁴, Q¹ and Q²are independently -M³L¹ _(Δ), or X⁴ is —Si(R⁸)—O-M³L¹ _(Δ), Q² is asingle bond joined to the silicon atom of X⁴ and Q¹ is -M⁴L⁴ _(Δ), or X⁴is —Si(R⁸)—O-M³L¹ _(Δ), Q² is a single bond joined to the silicon atomof X⁴ and Q¹ is a single bond joined to the M³ atom of X⁴.
 13. Thecomposition according to claim 1, wherein themetal-siloxane-silanol(ate) compound has the structural formula (II)

where Z¹, Z² and Z³ are independently selected from the group consistingof L², R⁵, R⁶ and R⁷, where L² is selected from the group consisting of—OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or—O—(C1- to C6-alkyl), or where L² is selected from the group consistingof —OH, —O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl,—O-isopropyl, and —O-isobutyl; R¹, R², R³ and R⁴ are independentlyselected from the group consisting of optionally substituted C1- toC20-alkyl, optionally substituted C3- to C8-cycloalkyl, optionallysubstituted C2- to C20-alkenyl and optionally substituted C5- toC10-aryl; and X⁴ is -M³L¹ _(Δ) or M³ and Q¹ and Q² are H or each is asingle bond joined to M³, where L¹ is selected from the group consistingof —OH and —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or—O—(C1- to C6-alkyl), or where L¹ is selected from the group consistingof —OH, —O— methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl,—O-isopropyl, and —O-isobutyl, and where M³ is selected from the groupconsisting of s- and p-block metals, d- and f-block transition metals,lanthanide and actinide metals and semimetals, especially from the groupconsisting of metals of transition groups 1, 2, 3, 4, 5, 8, 10 and 11and metals of main groups 1, 2, 3, 4 and 5, preferably from the groupconsisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi;especially preferably from the group consisting of Zn, Ti, Zr, Hf, V,Fe, Sn and Bi, or X⁴ is -M³L¹ _(Δ) and Q² is H or a single bond joinedto M³ and Q¹ is H, M⁴L⁴ _(Δ) or where M⁴ is selected from the groupconsisting of s- and p-block metals, d- and f-block transition metals,lanthanide and actinide metals and semimetals, especially from the groupconsisting of metals of transition groups 1, 2, 3, 4, 5, 8, 10 and 11and metals of main groups 1, 2, 3, 4 and 5, preferably from the groupconsisting of Na, Zn, Sc, Nd, Ti, Zr, Hf, V, Fe, Pt, Cu, Ga, Sn and Bi;especially preferably from the group consisting of Zn, Ti, Zr, Hf, V,Fe, Sn and Bi, and where L⁴ is selected from the group consisting of —OHand —O—(C1- to C10-alkyl), especially —O—(C1- to C8-alkyl) or —O—(C1- toC6-alkyl), or where L⁴ is selected from the group consisting of —OH,—O-methyl, —O-ethyl, —O-propyl, —O-butyl, —O-octyl, —O-isopropyl, and—O— isobutyl, and where R⁸ is selected from the group consisting ofoptionally substituted C1- to C20-alkyl, optionally substituted C3- toC8-cycloalkyl, optionally substituted C2- to C20-alkenyl and optionallysubstituted C5- to C10-aryl, or X⁴, Q¹ and Q² are independently -M³L¹_(Δ), or X⁴ is —Si(R⁸)—O-M³L¹ _(Δ), Q² is a single bond joined to thesilicon atom of X⁴ and Q¹ is -M¹L⁴ _(Δ), or X⁴ is —Si(R⁸)—O-M³L¹ _(Δ),Q² is a single bond joined to the silicon atom of X⁴ and Q¹ is a singlebond joined to the M³ atom of X⁴.
 14. The composition according to claim13, wherein the metal-siloxane-silanol(ate) compound is a metalsilsesquioxane of the structure (IV)

where X4 is selected from the group consisting of metals of transitiongroups 1, 2, 3, 4, 5, 8, 10 and 11 and metals of main groups 1, 2, 3, 4and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr,Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the groupconsisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, most preferably from thegroup consisting of Ti and Sn, and is most preferably Ti, and X4 isjoined to OR where R is selected from the group consisting of —H,-methyl, -ethyl, -propyl, -butyl, -octyl, -isopropyl, and -isobutyl, Z¹,Z² and Z³ are each independently C1- to C20-alkyl, C3- to C8-cycloalkyl,C2- to C20-alkenyl and C5- to C10-aryl, especially selected from thegroup consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl,hexyl, heptyl, octyl, vinyl, allyl, butenyl and phenyl, and benzyl, andR¹, R², R³ and R⁴ are each independently C1- to C20-alkyl, C3- toC8-cycloalkyl, C2- to C20-alkenyl, and C5- to C10-aryl, especiallyselected from the group consisting of methyl, ethyl, propyl, isopropyl,butyl, isobutyl, hexyl, heptyl, octyl, vinyl, allyl, butenyl and phenyl,and benzyl.
 15. The composition according to claim 14, wherein themetal-siloxane-silanol(ate) compound is a metal silsesquioxane of thestructure (IVb)

where X4 is selected from the group consisting of metals of transitiongroups 1, 2, 3, 4, 5, 8, 10 and 11 and metals of main groups 1, 2, 3, 4and 5, preferably from the group consisting of Na, Zn, Sc, Nd, Ti, Zr,Hf, V, Fe, Pt, Cu, Ga, Sn and Bi; especially preferably from the groupconsisting of Zn, Ti, Zr, Hf, V, Fe, Sn and Bi, most preferably from thegroup consisting of Ti (and therefore is heptaisobutyl POSS-titanium(IV)ethoxide (TiPOSS)) and Sn (and therefore is heptaisobutyl POSS-tin(IV)ethoxide (SnPOSS)), and is most preferably Ti (and therefore isheptaisobutyl POSS-titanium(IV) ethoxide (TiPOSS)).
 16. The compositionaccording to claim 1, wherein the silylated polymer (SiP) is obtainableby a synthesis, catalysed by a metal-siloxane-silanol(ate) compound, ofat least one isocyanate-reactive compound, especially at least onehydroxy-functionalized polymer (component A), and one or more compoundshaving at least one isocyanate group (component B).
 17. The compositionaccording to claim 16, wherein the metal-siloxane-silanol(ate) compoundfor catalysed synthesis of component A and component B is heptaisobutylPOSS-titanium(IV) ethoxide (TiPOSS) and/or heptaisobutyl POS S-tin(IV)ethoxide (SnPOSS), preferably heptaisobutyl POS S-titanium(IV) ethoxide(TiPOSS).
 18. The composition according to claim 1, wherein the polymerbackbone (P) of the silylated polymer (SiP) has constituents selectedfrom the group consisting of polyurethanes, polyureas, polyethers,polyesters, phenolic resins, polyalkylenes, poly(meth)acrylates,polyamides, polycaprolactones, polybutadienes or polyisoprenes, andpolycarbonates or mixtures thereof, preferably from the group consistingof polyurethanes, polyureas, poly(meth)acrylates or polyethers ormixtures thereof, most preferably polyethers.
 19. The compositionaccording to claim 1, wherein the silylated polymer (SiP) has at leasttwo end groups of the general formula (V)

where X is C, Si or a heteroatom and these, according to their valency,optionally have one or more R⁸ radicals, preferably C, N, O, P, S, morepreferably C, N or O, most preferably N or O, and each is bonded to acarbon in the polymer backbone, R* is O or an optionally substitutedstraight-chain or branched C1- to C25-alkyl group or an optionallysubstituted C4- to C18-cycloalkyl group or an optionally substituted C4-to C18-aryl group and, when R*=0, the silicon atom is bonded directly tothe nitrogen atom, each Y is independently either O or a direct bond ofthe silicon atom to the respective R⁹, R¹⁰ or R¹¹ radical, andpreferably at least one Y is O, R⁸ is H, an optionally substitutedstraight-chain or branched C1- to C16-alkyl group, an optionallysubstituted straight-chain or branched C2- to C16-alkenyl group or anoptionally substituted straight-chain or branched C2- to C16-alkynylgroup, an optionally substituted C4- to C14-cycloalkyl group or anoptionally substituted C4- to C14-aryl group, or a radical of thegeneral structure (Vb), R¹² and R¹⁴ are each independently H or aradical from the group consisting of —R¹⁵, —COOR¹⁵ and —CN, R¹³ is H ora radical from the group consisting of —CH₂—COOR¹⁵, —COOR¹⁵, —CONHR¹⁵,—CON(R¹⁵), —CN, —NO₂, —PO(OR¹⁵)₂, —SOR¹⁵ and —SO₂OR¹⁵, R¹⁵ is ahydrocarbyl radical having 1 to 20 carbon atoms and optionally having atleast one heteroatom, R⁹, R¹⁰ and R¹¹ are independently H, an optionallysubstituted straight-chain or branched C1- to C5-alkyl group, anoptionally substituted straight-chain or branched C2- to C10-alkenylgroup or an optionally substituted C4- to C14-cycloalkyl group or anoptionally substituted C4- to C14-aryl group, m is 0 or 1 and, when m=0,the silicon atom is bonded directly to a carbon in the polymer backbone(P).
 20. The composition according to claim 19, wherein the silylatedpolymer (SiP) has a polyether polymer backbone having at least two endgroups of the general formula (V)

where X is N or O and N optionally has an R⁸ radical, R* is 0 or anoptionally substituted straight-chain or branched C1- to C20-alkyl groupor an optionally substituted C4- to C12-cycloalkyl group or anoptionally substituted C4- to C12-aryl group, preferably an optionallysubstituted straight-chain or branched C1- to C15-alkyl group, and, whenR*=0, the silicon atom is bonded directly to the nitrogen atom, Y inY—R⁹ and Y—R¹⁰ are O and the Y in Y—R¹¹ is either O or a direct bond ofthe silicon atom to the respective R¹¹ radical, R⁸ is H, an optionallysubstituted straight-chain or branched C1- to C10-alkyl group, anoptionally substituted straight-chain or branched C2- to C10-alkenylgroup or an optionally substituted straight-chain or branched C2- toC10-alkynyl group, an optionally substituted C4- to C10-cycloalkyl groupor an optionally substituted C4- to C10-aryl group or a succinic acidderivative of the general structure (Vb), R⁹, R¹⁰ and R¹¹ areindependently H, an optionally substituted straight-chain or branchedC1- to C4-alkyl group, an optionally substituted straight-chain orbranched C2- to C5-alkenyl group or an optionally substituted C4- toC10-cycloalkyl group or an optionally substituted C4- to C10-aryl group,preferably independently H or a C1- to C2-alkyl group, and m is 0 or 1and, when m=0, the silicon atom is bonded directly to a carbon in thepolymer backbone (P), preferably m=1.
 21. The composition according toclaim 20, wherein the silylated polymer (SiP) has a polyether polymerbackbone having at least two end groups of the general formula (V)

where R* is 0 or an optionally substituted straight-chain or branchedC1- to C15-alkyl group or an optionally substituted C4- to C6-cycloalkylgroup or an optionally substituted C4- to C6-aryl group, preferably anoptionally substituted straight-chain or branched C1- to C10-alkylgroup, more preferably a C1-alkyl group (=alpha-silane) or a C3-alkylgroup (=gamma-silane), and, when R*=0, the silicon atom is bondeddirectly to the nitrogen atom, R⁸ is H, an optionally substitutedstraight-chain or branched C1- to C8-alkyl group, an optionallysubstituted straight-chain or branched C2- to C8-alkenyl group or anoptionally substituted straight-chain or branched C2- to C8-alkynylgroup, an optionally substituted C4- to C6-cycloalkyl group or anoptionally substituted C4- to C6-aryl group, R⁹, R¹⁰ and R¹¹ areindependently H, an optionally substituted straight-chain or branchedC1- to C4-alkyl group, an optionally substituted straight-chain orbranched C2- to C5-alkenyl group or an optionally substituted C4- toC6-cycloalkyl group or an optionally substituted C4- to C6-aryl group,preferably independently H or a C1- to C2-alkyl group, and m is 0 or 1and, when m=0, the silicon atom is bonded directly to a carbon in thepolymer backbone (P), preferably m=1.
 22. The composition according toclaim 16, wherein the hydroxy-functionalized polymer is selected fromthe group consisting of polyoxyalkylene diols or polyoxyalkylene triols,especially polyoxyethylene di- and triols and polyoxypropylene di- andtriols, higher-functionality polyols such as sorbitol,pentaerythritol-started polyols, ethylene oxide-terminatedpolyoxypropylene polyols, polyester polyols, styrene-acrylonitrile,acryloyl-methacrylate, (poly)urea-grafted or -containing polyetherpolyols, polycarbonate polyols, CO₂ polyols, polyhydroxy-functional fatsand oils, especially castor oil, polyhydrocarbon polyols such asdihydroxypolybutadiene, polytetrahydrofuran-based polyethers (PTMEG),OH-terminated prepolymers based on the reaction of a polyetherol orpolyesterol with a diisocyanate, polypropylene diols, polyester polyolsor mixtures thereof, preferably polypropylene diols, polyester polyols,or mixtures thereof.
 23. The composition according to claim 22, whereinthe hydroxy-functionalized polymer is selected from the group consistingof polyoxyalkylene diols, polyoxyalkylene triols, especiallypolyoxyethylene di- and/or triols and/or polyoxypropylene di- and/ortriols, KOH-catalysed hydroxy-functionalized polyethers or double metalcyanide complex-catalysed (DMC-catalysed) hydroxy-functionalizedpolyethers or mixtures thereof.
 24. The composition according to claim16, wherein component B is selected from the group consisting ofaromatic and/or aliphatic isocyanates (Iso) of the general structure(VI) or mixtures thereof or isocyanatosilanes (Iso-Si) of the generalstructure (VII) or mixtures thereof

where R^(x) is a carbon-containing group, preferably at least onearomatic or aliphatic group or mixtures thereof, more preferably anoptionally substituted straight-chain or branched C1- to C16-alkylgroup, an optionally substituted straight-chain or branched C2- toC16-alkenyl group or an optionally substituted straight-chain orbranched C2- to C16-alkynyl group, an optionally substituted C4- toC14-cycloalkyl group or an optionally substituted C4- to C14-aryl group,most preferably diphenylmethane, toluene, dicyclohexylmethane, hexane ormethyl-3,5,5-trimethylcyclohexyl, each Y is independently either O or adirect bond of the silicon atom to the respective R⁹, R¹⁰ or R¹¹radical, and preferably at least one Y is O, z is at least 1, preferablyat least 2, R⁹, R¹⁰ and R¹¹ are independently H, an optionallysubstituted straight-chain or branched C1- to C5-alkyl group, anoptionally substituted straight-chain or branched C2- to C10-alkenylgroup or an optionally substituted C4- to C8-cycloalkyl group or anoptionally substituted C4- to C8-aryl group and R* is 0 or an optionallysubstituted straight-chain or branched C1- to C25-alkyl group or anoptionally substituted C4- to C18-cycloalkyl group or an optionallysubstituted C4- to C18-aryl group and, when R*=0, the silicon atom isbonded directly to the nitrogen atom.
 25. The composition according toclaim 16, wherein component B is selected from the group consisting ofaromatic and/or aliphatic isocyanates (Iso) of the general structure(VI) or mixtures thereof or isocyanatosilanes (Iso-Si) of the generalstructure (VII) or mixtures thereof

where R^(x) is diphenylmethane, toluene, dicyclohexylmethane, hexane ormethyl-3,5,5-trimethylcyclohexyl, preferably diphenylmethane or hexaneor methyl-3,5,5-trimethylcyclohexyl, most preferably diphenylmethane ormethyl-3,5,5-trimethylcyclohexyl, and z is at least 2, preferably 2, Yin Y—R⁹ and Y—R¹⁰ are O and the Y in Y—R¹¹ is either O or a direct bondof the silicon atom to the respective R¹¹ radical, R⁹, R¹⁰ and R¹¹ areindependently H, an optionally substituted straight-chain or branchedC1- to C3-alkyl group and R* is 0 or an optionally substitutedstraight-chain or branched C1- to C15-alkyl group or an optionallysubstituted C4- to C6-cycloalkyl group or an optionally substituted C4-to C6-aryl group, preferably an optionally substituted straight-chain orbranched C1- to C10-alkyl group, more preferably a C1-alkyl group(=alpha-silane) or a C3-alkyl group (=gamma-silane), and, when R*=0, thesilicon atom is bonded directly to the nitrogen atom.
 26. Thecomposition according to claim 25, wherein Component B is at least oneisocyanate (Iso) of the general structure (VI) selected from the groupconsisting of polymeric, oligomeric and monomeric methylene diphenylisocyanate (MDI), especially from 4,4′-methylene diphenyl isocyanate(4,4′-MDI), 2,4′-methylene diphenyl isocyanate (2,4′-MDI),2,2′-methylene diphenyl isocyanate (2,2′-MDI),4,4′-diisocyanatodicyclohexylmethane (H12MDI), 2-methylpentamethylene1,5-diisocyanate, dodecamethylene 1,12-diisocyanate, lysine and lysineester diisocyanate, cyclohexane 1,3-diisocyanate, cyclohexane1,4-diisocyanate, perhydro(diphenylmethane 2,4′-diisocyanate),perhydro(diphenylmethane 4,4′-diisocyanate),1,4-diisocyanato-2,2,6-trimethylcyclohexane (TMCDI),3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (=isophoronediisocyanate or IPDI), hexamethylene 1,6-diisocyanate (HDI) or thetrimer thereof (HDI trimer), 2,2,4- and/or 2,4,4-trimethylhexamethylene1,6-diisocyanate, 1,4-bis(isocyanato)cyclohexane,1,4-bis(isocyanato)benzene (PPDI), 1,3- and/or1,4-bis(isocyanatomethyl)cyclohexane, m- and/or p-xylylene diisocyanate(m- and/or p-XDI), m- and/or p-tetramethylxylylene 1,3-diisocyanate, m-and/or p-tetramethylxylylene 1,4-diisocyanate,bis(1-isocyanato-1-methylethyl)naphthalene,1,3-bis(isocyanato-4-methylphenyl)-2,4-dioxo-1,3-diazetidine,naphthalene 1,5-diisocyanate (NDI),3,3′-dimethyl-4,4′-diisocyanatodiphenyl (TODI), tolylene 2,4- and/or2,6-diisocyanate (TDI), 1,3-bis(isocyanatomethyl)benzene or mixturesthereof, preferably 4,4′-methylene diphenyl isocyanate (4,4′-MDI) orisophorone diisocyanate (IPDI), hexamethylene 1,6-diisocyanate (HDI) orthe trimer thereof (HDI trimer) or mixtures thereof, most preferably4,4′-methylene diphenyl isocyanate (4,4′-MDI) or isophorone diisocyanate(IPDI) or mixtures thereof.
 27. The composition according to claim 26,wherein Component B is at least one isocyanatosilane (Iso-Si) of thegeneral structure (VII), or mixtures thereof,

where R⁹, R¹⁰, and R¹¹ a methyl or ethyl group or mixtures thereof,preferably selected from the group consisting of 3-(triethoxysilyl)methyl isocyanate, 3-(trimethoxysilyl)methyl isocyanate,3-(triethoxy silyl)ethyl isocyanate, 3-(trimethoxysilyl)ethylisocyanate, 3-(triethoxysilyl)propyl isocyanate,3-(trimethoxysilyl)propyl isocyanate, 3-(triethoxy silyl)butylisocyanate, 3-(trimethoxysilyl)butyl isocyanate,3-(triethoxysilyl)pentyl isocyanate, 3-(trimethoxysilyl)pentylisocyanate, 3-(triethoxysilyl)hexyl isocyanate, 3-(trimethoxysilyl)hexylisocyanate or mixtures thereof, preferably 3-(trimethoxysilyl)methylisocyanate, 3-(triethoxysilyl)methyl isocyanate,3-(trimethoxysilyl)propyl isocyanate, 3-(triethoxysilyl)propylisocyanate or mixtures thereof, more preferably3-(trimethoxysilyl)propyl isocyanate, 3-(triethoxysilyl)propylisocyanate, or mixtures thereof.
 28. The composition according to claim1, wherein the silylated polymer (SiP) has been prepared by reactionwith an aminosilane (AmSi).
 29. The composition according to claim 28,wherein the aminosilane (AmSi) is at least one aminosilane (AmSi) of thegeneral structure (VIII), or is a mixture thereof,

where R⁷ is H, R⁸ is H, an optionally substituted straight-chain orbranched C1- to C25-alkyl group, an optionally substitutedstraight-chain or branched C2- to C25-alkenyl group or an optionallysubstituted C4- to C18-cycloalkyl group or an optionally substituted C4-to C18-aryl group, or a radical of the general structure (Vb), R* is 0or an optionally substituted straight-chain or branched C1- to C25-alkylgroup or an optionally substituted C4- to C18-cycloalkyl group or anoptionally substituted C4- to C18-aryl group and, when R*=0, the siliconatom is bonded directly to the nitrogen atom, R¹² and R¹⁴ are eachindependently H or a radical from the group consisting of —R¹⁵, —COOR¹⁵and —CN, R¹³ is H or a radical from the group consisting of —CH₂—COOR¹⁵,—COOR¹⁵, —CONHR¹⁵, —CON(R¹⁵), —CN, —NO₂, —PO(OR¹⁵)₂, —SOR¹⁵ and—SO₂OR¹⁵, R¹⁵ is a hydrocarbyl radical having 1 to 20 carbon atoms andoptionally having at least one heteroatom, R⁹, R¹⁰ and R¹¹ areindependently H, an optionally substituted straight-chain or branchedC1- to C4-alkyl group, an optionally substituted straight-chain orbranched C2- to C5-alkenyl group or an optionally substituted C4- toC10-cycloalkyl group or an optionally substituted C4- to C10-aryl group,preferably independently H or a C1-to C2-alkyl group, and each Y isindependently either O or a direct bond of the silicon atom to therespective R⁹, R¹⁰ or R¹¹ radical, and preferably at least one Y is O.30. The composition according to claim 29, wherein the aminosilane(AmSi) of the general structure (VIII) is selected from the group ofN-[3-(trimethoxysilyl)methyl]butylamine,N-[3-(triethoxysilyl)methyl]butylamine,N-[3-(trimethoxysilyl)ethyl]butylamine,N-[3-(triethoxysilyl)ethyl]butylamine,N-[3-(trimethoxysilyl)propyl]butylamine,N-[3-(triethoxysilyl)propyl]butylamine,N-[3-(trimethoxysilyl)butyl]butylamine,N-[3-(triethoxysilyl)butyl]butylamine,N-[3-(trimethoxysilyl)pentyl]butylamine,N-[3-(triethoxysilyl)pentyl]butylamine,N-[3-(trimethoxysilyl)hexyl]butylamine,N-[3-(triethoxysilyl)hexyl]butylamine, 3-aminopropyltrimethoxysilane,3-aminopropyltriethoxysilane,N-cyclohexyl-3-aminopropyltrimethoxysilane,N-cyclohexyl-3-aminopropyltriethoxysilane,N-(3-trimethoxysilylpropyl)aminosuccinic acid diethyl ester,N-(3-triethoxysilylpropyl)aminosuccinic acid diethyl ester or a mixturethereof, preferably N-[3-(trimethoxysilyl)methyl]butylamine,N-[3-(triethoxysilyl)methyl]butylamine,N-[3-(trimethoxysilyl)propyl]butylamine,N-[3-(triethoxysilyl)propyl]butylamine,N-(3-trimethoxysilylpropyl)aminosuccinic acid diethyl ester,N-(3-triethoxysilylpropyl)aminosuccinic acid diethyl ester, morepreferably N-[3-(trimethoxysilyl)propyl]butylamine,N-[3-(triethoxysilyl)propyl]butylamine,N-[3-(trimethoxysilyl)methyl]butylamine,N-[3-(triethoxysilyl)methyl]butylamine,N-(3-triethoxysilylpropyl)aminosuccinic acid diethyl ester,N-(3-trimethoxysilylpropyl)aminosuccinic acid diethyl ester or a mixturethereof, most preferably N-(3-triethoxysilylpropyl)aminosuccinic aciddiethyl ester, N-[3-(triethoxysilyl)propyl]butylamine,N-[3-(triethoxysilyl)methyl]butylamine or a mixture thereof. 31.(canceled)